Solvent-free enyne metathesis polymerization

ABSTRACT

The disclosure describes methods of metathesizing unsaturated organic compounds, each method comprising contacting at least one feedstock comprising at least one olefinic or acetylenic precursor with a solid transition metal-based metathesis catalyst in the absence of a liquid solvent or precursor to form a polymer product.

CROSS REFERENCE TO RELATED APPLICATIONS

This Application claims the benefit of U.S. Provisional Application Ser. No. 61/678,484, filed Aug. 1, 2012, which is incorporated by reference in its entirety.

TECHNICAL FIELD

The present invention relates to polymer-forming metathesis reactions catalyzed by organometallic coordination compounds. The present invention also relates to ruthenium phosphine complexes.

BACKGROUND

Olefin metathesis is a useful tool in preparing a range of polymeric and non-polymeric intermediates and products for products ranging from pharmaceuticals to organic semiconductors. In part, due to the efficiency of the available catalysts, current synthetic methods for preparing discrete, non-polymeric compounds are generally accomplished using solution-based systems. Polymers may also be prepared using solution-based systems, but more recently, experimentalists have also used methods using vapor phase reactions. The reaction conditions associated with such reactions—sublimation or vapor phase liquid transfer—results in conditions where localized condensation occurs at the site of catalytic activity. These localized solvent effects give rise to variation of growth rates, orientations of individual polymer strands within an array of growing polymers, or both. In certain applications, for example in organic semiconductor devices, reducing such variability is important for more consistent performance. The present invention is directed to addressing one or more of the aforementioned concerns.

SUMMARY

The present inventions are directed to methods of metathesizing unsaturated organic compounds, each method comprising contacting at least one feedstock vapor or gas comprising at least one olefinic or acetylenic precursor with a solid transition metal-based metathesis catalyst to form a polymer product, wherein the transition metal-based metathesis catalyst is in a solid form and the contacting is done in the absence of a liquid. In specific independent embodiments, the methods employ direct gas/solid phase polymerization reactions, avoiding the presence of bulk or localized liquids at the site of catalytic activity, and the product polymer is formed by an enyne, diyne, or ring opening metathesis polymerization (ROMP) reaction. The methods may be operable at near ambient conditions, using a range of metathesis catalysts, including various versions of the Grubbs' catalysts.

In addition to the methods, the inventions are directed to the compositions which result from operating the inventive methods. These compositions may be free-standing polymer-containing compositions or compositions in which the polymer is attached, or tethered, to a surface. This disclosure further described devices derived from such methods and compositions, for example, polymer electronic devices (e.g. diodes, capacitors, chemical sensors, light emitting diodes (LEDs), photodetectors, photovoltaic cells, thermoelectric detectors, or transistors), medical implants, composite materials, antireflection coatings, antifouling coatings, microfluidics, and reactor modification for chemical synthesis.

BRIEF DESCRIPTION OF THE DRAWINGS

The present application is further understood when read in conjunction with the appended drawings. For the purpose of illustrating the subject matter, there are shown in the drawings exemplary embodiments of the subject matter; however, the presently disclosed subject matter is not limited to the specific methods, devices, and systems disclosed. In addition, the drawings are not necessarily drawn to scale. In the drawings:

FIG. 1 provides an illustration of the proposed mechanism described specifically in Example 3.

FIG. 2 shows a micrograph of a sample prepared as described in Example 3.

FIG. 3A provides an illustration of the structure of the device prepared in Example 4.

FIG. 3B illustrates the energy levels before equilibration (not in contact) of the three constituent materials of Example 4. The proposed effect of the dipole of a Self-Assembled Monolayer of Phosphonate (SAMP) is shown. This is designed to lower the work function of the Al electrode to above the electron affinity of polyacetylene, to access inversion.

FIG. 3C shows the relationship between current and applied voltage for the device prepared in Example 4.

DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

The present invention may be understood more readily by reference to the following description taken in connection with the accompanying Figures and Examples, all of which form a part of this disclosure. It is to be understood that this invention is not limited to the specific products, methods, conditions or parameters described or shown herein, and that the terminology used herein is for the purpose of describing particular embodiments by way of example only and is not intended to be limiting of any claimed invention. Similarly, unless specifically otherwise stated, any description as to a possible mechanism or mode of action or reason for improvement is meant to be illustrative only, and the invention herein is not to be constrained by the correctness or incorrectness of any such suggested mechanism or mode of action or reason for improvement. Throughout this text, it is recognized that the descriptions refer to compositions and methods of making and using said compositions. That is, where the disclosure describes or claims a feature or embodiment associated with a composition or a method of making or using a composition, it is appreciated that such a description or claim is intended to extend these features or embodiment to embodiments in each of these contexts (i.e., compositions, methods of making, and methods of using).

In the present disclosure the singular forms “a,” “an,” and “the” include the plural reference, and reference to a particular numerical value includes at least that particular value, unless the context clearly indicates otherwise. Thus, for example, a reference to “a material” is a reference to at least one of such materials and equivalents thereof known to those skilled in the art, and so forth.

When a value is expressed as an approximation by use of the descriptor “about,” it will be understood that the particular value forms another embodiment. In general, use of the term “about” indicates approximations that can vary depending on the desired properties sought to be obtained by the disclosed subject matter and is to be interpreted in the specific context in which it is used, based on its function. The person skilled in the art will be able to interpret this as a matter of routine. In some cases, the number of significant figures used for a particular value may be one non-limiting method of determining the extent of the word “about.” In other cases, the gradations used in a series of values may be used to determine the intended range available to the term “about” for each value. Where present, all ranges are inclusive and combinable. That is, references to values stated in ranges include every value within that range.

It is to be appreciated that certain features of the invention which are, for clarity, described herein in the context of separate embodiments, may also be provided in combination in a single embodiment. That is, unless obviously incompatible or specifically excluded, each individual embodiment is deemed to be combinable with any other embodiment(s) and such a combination is considered to be another embodiment. Conversely, various features of the invention that are, for brevity, described in the context of a single embodiment, may also be provided separately or in any sub-combination. Finally, while an embodiment may be described as part of a series of steps or part of a more general structure, each said step may also be considered an independent embodiment in itself, combinable with others.

The transitional terms “comprising,” “consisting essentially of,” and “consisting” are intended to connote their generally in accepted meanings in the patent vernacular; that is, (i) “comprising,” which is synonymous with “including,” “containing,” or “characterized by,” is inclusive or open-ended and does not exclude additional, unrecited elements or method steps; (ii) “consisting of” excludes any element, step, or ingredient not specified in the claim; and (iii) “consisting essentially of” limits the scope of a claim to the specified materials or steps “and those that do not materially affect the basic and novel characteristic(s)” of the claimed invention. Embodiments described in terms of the phrase “comprising” (or its equivalents), also provide, as embodiments, those which are independently described in terms of “consisting of” and “consisting essentially” of. For those embodiments provided in terms of “consisting essentially of,” the basic and novel characteristic(s) is the operability of the methods (or the compositions or devices derived therefrom) as a direct gas/solid phase reaction.

When a list is presented, unless stated otherwise, it is to be understood that each individual element of that list, and every combination of that list, is a separate embodiment. For example, a list of embodiments presented as “A, B, or C” is to be interpreted as including the embodiments, “A,” “B,” “C,” “A or B,” “A or C,” “B or C,” or “A, B, or C.”

Throughout this specification, words are to be afforded their normal meaning, as would be understood by those skilled in the relevant art. However, so as to avoid misunderstanding, the meanings of certain terms will be specifically defined or clarified.

The present invention includes embodiments related to methods of metathesizing olefinic or acetylenic precursors using transition metal-based metathesis catalysts and the products deriving from such methods, and devices made from such products. Among the embodiments of the present invention are methods of metathesizing unsaturated organic compounds, each method comprising contacting at least one feedstock vapor or gas comprising at least one olefinic or acetylenic precursor with a solid transition metal-based metathesis catalyst to form a polymer product, wherein the transition metal-based metathesis catalyst is in a solid form (i.e., undissolved in a solvent or liquid precursor) and the contacting is done in the absence of a liquid (including solvent or precursor). That is, as contemplated herein, such that the olefinic or acetylenic precursor is presented to the solid transition metal-based metathesis catalyst as a vapor or gas. As used herein, the terms “gas” and “vapor” are distinguished, in that the term “gas” is used to describe a condition where the partial pressure of the precursor organic compound is less than the saturated vapor pressure for that material at the conditions applied during the polymerization reaction, whereas the term “vapor” refers to a condition where the precursor compound is at or above the saturated vapor pressure at the conditions applied for the metathesis. Separate additional independent embodiments provide that the term gas refers to a condition wherein the partial pressure of precursor compound is in a range having a lower value of about 0.001%, about 0.01%, about 0.1%, about 1%, 5%, about 10%, about 25%, or about 50% and an upper value of about 99%, about 95%, about 90%, about 80%, about 75%, about 50%, about 25%, about 10%, about 5%, about 2%, or about 1% of the saturated vapor pressure for that material at the conditions applied during the polymerization reaction. Exemplary, non-limiting, ranges include from about 0.1% to about 1%, from about 1% to about 5%, from 1% to about 10%, from about 5% to about 10%, and from about 5% to about 25%, of the saturated vapor pressure for that material at the conditions applied during the polymerization reaction. Accordingly, reactions involving subliming solids, or other reaction conditions wherein the volatilized precursor compound are in equilibrium with its corresponding solid or liquid phase are considered to involve vapor phase, and not gas phase, conditions. The term “gas” is also intended to include those materials at conditions above their critical points—i.e., supercritical conditions. The direct vapor/solid phase and direct gas/solid phase polymerization reactions are considered to be independent variants of the general invention. While both are considered within the scope of the present disclosure, direct gas/solid phase polymerization reactions are preferred. To the knowledge of the inventors, at least the direct gas/solid phase polymerization reactions described herein are unprecedented using metathesis catalysts.

Also, and as will become apparent during the following discussion, and while not intending to be bound by the correctness of the theory described herein, the technology may be envisioned in terms that the growing polymer material is comprised of an individual polymer chain or an array of polymer chains with a living layer of catalyst at the surface (or at the “distal ends” of the “growing” polymer chains). While not requiring that the growing polymer(s) is/are attached to any surface, one advantage of such a phenomenon, is that it enables imprinting of a surface pattern/texture/etc. (either physisorbed or chemically tethered) onto the material being grown. It also enables the living catalyst layer at the surface to be used for further functionality (e.g., in making blocks for block copolymers, recycling the catalyst, and in transforming the catalyst to make functionalized or further active termini). This is very much distinguished from a solution-phase reaction, or even a vapor phase reaction, where solvation leads to a greater degree of reorganization/diffusion of the living catalyst species—and thus randomization (loss of surface “memory”) of the polymer material being grown.

Returning again to some embodiments of the invention, and as described above, each method comprises contacting at least one feedstock vapor or gas comprising at least one olefinic or acetylenic precursor with a solid transition metal-based metathesis catalyst to form a polymer product, wherein the transition metal-based metathesis catalyst is in a solid form and the contacting is done under direct vapor/solid phase and direct gas/solid phase polymerization reaction conditions. In certain embodiments, the product polymer is formed by a mechanism comprising an enyne reaction, a diyne reaction, a ring opening metathesis polymerization (ROMP) reaction, or a combination or each type of reaction, though it should be appreciated that the teachings described herein may be applied to and incorporate other types of metathesis reactions (e.g., cross metathesis reactions). In preferred embodiments, the method provides that the product polymer results from at least partial polymerization of an acetylene (especially acetylene itself) by an enyne (or diyne) mechanism. That is, the methods provide for direct gas/solid phase polymerization reactions incorporating acetylenic precursors into either random or block copolymers, along with other non-acetylenic precursors. For example, certain independent embodiments provide that at least one of the feedstocks may independently comprise at least one olefinic precursor, or at least one acetylenic precursor, or a mixture of one or more olefinic and acetylenic precursors. Other embodiments provide that the product polymer may derive from application of a singly applied feedstock or a plurality of feedstocks applied sequentially. That is, the polymerization can be paused by reducing the amount of available feedstock precursors, eliminating free feedstock precursors, or transferring the polymerization to a new environment. The polymerization can be resumed by reintroducing the same or different feedstock precursors to the previously formed polymer chains. Similarly, the polymerization can be stopped by exposing the polymer chains to a chain transfer agent. Chain transfer agents transfer the catalyst from a growing polymer chain to the chain transfer agent. Since the polymerization occurs at the terminal, distal end of the polymer chain(s), the use of a chain transfer agent results in all or a portion of the chain transfer agent being bonded to the end to the polymer chains. This enables one to functionalize the terminal, distal ends of the growing polymer strands and, where present as a plurality of polymer strands, the surface of the polymeric material. Illustrative functionalized chain transfer agents include those represented by a general formula X—CH═CH—Y, where X and Y may be the same or different. These chain transfer agents may include, but are not limited to, symmetrical internal olefins or vinyl ethers. These chain transfer agents may also be optionally substituted, such as substituted with an amino, carbene, carboxylate, catecholate, a dithiocarbamate, dithioic acid, hydroxy, hydroxyamic acid, isocyanato, nitrite, phosphate, phosphonate, a silane or silicate, or thiol groups, or any combination thereof.

The skilled artisan would appreciate the various types of polymer classes that such options present. For example, application of a single feedstock would results in a homopolymer derived from the monomers of that precursor; e.g., where only acetylene is used, the product polymer would be polyacetylene. In another example, application of a single feedstock comprising a mixture of at least one olefinic precursor, or at least one acetylenic precursor, or a mixture of one or more olefinic and acetylenic precursors would result in either a random copolymer, a partial block copolymer, or a pure block copolymer, the exact nature of which depending on the relative concentrations and reactivities of the respective monomer precursors. In yet another application, sequential applications of individual feedstocks comprising, for example, an olefinic precursor, an acetylenic precursor, and a different acetylenic precursor would result in a deliberately engineered block copolymer. In those cases where multiple steps are involved, it is not necessary that every application employs the inventive steps described herein to be considered within the scope of the present invention, so long as one application does. These examples are not intended to be limiting, but representative of possible options, and again the specific design of the product polymers would be within the skill and control of the person of ordinary skill in the art, using the teachings presented here.

As described herein, in certain embodiments, the methods provide polyacetylene polymers or blocks within block co-polymers. Depending on the choice of reaction conditions, for example temperature, pressure, and choice of catalyst (see, e.g., below), in some of these embodiments, the polyacetylene may form in a substantially cis-conformation (i.e., as a cis-polyacetylene polymer or block) and in other embodiments in a substantially trans-conformation (i.e., as trans-polyacetylene polymer or block). Similar experimental modifications may be employed to provide that the incorporated olefins adopt similar cis- or trans-conformations.

The methods may use precursors that contain electron donor substituents, electron acceptor substituents, or both, such that the precursor, when polymerized, is capable of forming a semiconducting polymer or polymer block that acts as an electron donor, acceptor, or both. Note that the ability to prepare block copolymers comprising separate donor/acceptor blocks offers the possibility of forming p-n junctions to use as diodes and the like. Suitable precursors are those which provide polymers that are electron acceptors or donors or semiconducting organometallic polymers that are electron acceptors or electron donors or emitters. As described herein, these methods can be modified to provide polymers or polymer blocks that are doped to behave as a p-type semiconductors or an n-type semiconductor. Especially suitable precursors are those which are capable of providing polyacetylenes, polypyrroles, polyanilines, poly(thienylenevinylene)s, polythiophenes, and poly(phenylenevinylene)s, any of which can be substituted or unsubstituted and branched or unbranched. As describes elsewhere herein, a particularly useful example of precursor is acetylene, capable of providing polyacetylenes.

The methods can be used to provide polymer products of virtually any length, individual embodiments described some such lengths as being within a range having a lower value of about 5 nm, about 10 nm, about 50 nm, about 100 nm, about 500 nm, or about 1000 nm and an upper value of about 10,000 nm, about 5000 nm, about 1000 nm, about 500 nm, about 100 nm, or about 50 nm. Illustrative, non-limiting ranges, then, can include those from about 10 nm to about 10,000 nm, about 10 nm to 1000 nm, or about 50 nm to about 500 nm.

Stated differently, the methods can be used to provide polymer products (including polymers or polymer blocks) which are not intrinsically limited by the number of repeating units. However, so as to specify some limits, certain embodiments provide that the methods independently provide polymers or polymer blocks having at least about 5, 50, or 500 repeating units, less than 500,000, 50,000, or 5000 repeating units, or any combination thereof.

One of the many advantages of the present invention is that the rate at which the different polymer chains grow is more consistent than seen in traditional chain polymerization reactions. The similarity in growth rate for each individual polymer strand results in chains of very similar lengths. In separate embodiments, at least about 50%, 60%, 70%, 80%, or at least about 90% of the formed product polymer chains have lengths within 50 nm, 25 nm or 10 nm of their average length.

The methods may further comprise steps which comprise co-depositing, or sequentially stepwise depositing nanoparticles or other materials, during or following a metathesis reaction. Unless otherwise specified, nanoparticles include those particles or fibrils having a least one dimension in a range of from about 1 nm to about 1000 nm. Additional independent embodiments provide that such particles may have such particle dimensions in a range having a lower value of about 1 nm, about 2 nm, about 5 nm, about 10 nm, or about 50 nm and an upper value of about 1000 nm, about 800 nm, about 600 nm, about 400 nm, about 200 nm, or about 100 nm, with exemplary ranges including those from about 2 nm to about 100 nm, from 2 nm, or from bout to about 50 nm, or a range of from about 5 nm to about 10 nm. In the context of the present invention, nanoparticles may be organic or inorganic and may include, but are not limited to, nanotubes, magnetic nanoparticles and quantum dots.

Since, as suggested above, the polymerization can be paused at nearly any point in the reaction and then resumed, a layer of nanoparticles can optionally be formed on the partially formed active polymer chains while the polymerization is paused. When the polymerization is resumed, the active polymer chains can extend through interstices in the nanoparticles. The ability to pause the polymerization at nearly any point in the polymerization allows one or more layers of the nanoparticles to be positioned anywhere along the length of the active polymer chains. For instance, a layer of the nanoparticles can be positioned such that the p-n junctions are positioned in the interstices of the nanoparticles. Additionally, the nanoparticles can be selected to scatter incident light. When the nanoparticles are positioned to scatter this light near the p-n junctions, the amount of light absorbed near the p-n junctions can be increased in order to further enhance the efficiency of the device. In addition to scattering light or as an alternative to scattering light, the nanoparticles can increase optical density near the nanoparticles as a result of the nanoparticles behaving as an antenna. When the nanoparticles are positioned to enhance light density near the p-n junctions, the amount of light absorbed near the p-n junctions can be increased in order to further enhance the efficiency of the device.

The methods may further comprise steps which comprise co-depositing, or sequentially stepwise depositing other materials during or following a metathesis reaction. Such “other materials” may include species which may act as a dopant in the final form product. Iodine is one such exemplary molecule, having sufficient volatility to be useful in this capacity. Similarly, metals or other conductors may be deposited onto the polymer products.

As described above, among the embodiments of the present invention are those methods in which the metathesis reactions are described in terms direct vapor/solid phase and direct gas/solid phase polymerization, preferably the latter. One advantage of the inventive methods is that the metatheses can be conducted under miler conditions under relatively milder conditions, relative the corresponding solvent-based or uncatalyzed reactions. That said, various embodiments include those where the metathesis reaction is carried out under conditions where the at least one olefinic or acetylenic precursor has a partial pressure in a range of from about 0.1 psia to about 300 psia, at a temperature in a range of from about −10° C. to about 300° C., or both. The methods may still be operable outside of these ranges, though one would expect that these conditions would be at the expense of any useful kinetics. In other independent embodiments, the methods may be practiced at precursor partial pressures bounded by ranges in which the lower value is about 0.1, about 0.5, about 1, about 2, about 3, about 4, about 5, about 6, about 7, about 8, about 9, about 10, about 15, about 20, about 25, about 30, about 40, about 50, about 60, about 70, about 80, about 90, or about 100 psia and the upper value of the range is about 10, about 20, about 30, about 40, about 50, about 60, about 80, about 100, about 120, about 140, about 160, about 180, or about 200 psia. Likewise, the methods may be practiced at temperatures bounded by ranges in which the lower value is about −10° C., about 0° C., about 20° C., about 40° C., about 60° C., about 80° C., or about 100° C., and the upper end of the range is about 300° C., about 275° C., about 250° C., about 225° C., about 200° C., about 180° C., about 160° C., about 140° C., about 120° C., about 120° C., or about 100° C. As the skilled artisan will appreciate, the choice of operating conditions, particularly temperature, will depend on a number of factors, including the nature of the organic precursors and the transition metal catalysts, through the skilled artisan would be able to define these without undue experimentation.

Acetylenic Precursors

The methods herein are described in terms of at least one feedstock comprising at least one olefinic or acetylenic precursor. In principle, these feedstocks may comprise precursors comprising cyclic or alicyclic cis- or trans-alkenes or compounds containing an alkyne linkage. Since methods employing direct gas/solid phase polymerization reactions are preferred, those precursors that are sufficiently volatile under the reactions conditions described below as to be present in the gas phase (as contrasted to the vapor phase) are also preferred. Also as suggested elsewhere herein, given the preference for products accessible by enyne or diyne reaction mechanisms, optionally substituted acetylenes (alkynyl compounds) are particularly suitable, and in some cases necessary, precursors for these methods. Lower alkynyl (acetylenic) compounds are particularly suitable. As used herein, the term “alkynyl” (or “acetylenic”) or “alkyne” refers to a linear or branched hydrocarbon group or compound of 2 to about 24 carbon atoms containing at least one triple bond, such as ethynyl, n-propynyl, and the like. Preferred alkynyl groups herein contain 2 to about 12 carbon atoms, preferably containing a terminal alkyne bond. The term “lower alkynyl” refers to an alkynyl group of 2 to 6 carbon atoms. The term “substituted alkynyl” refers to alkynyl substituted with one or more substituent groups. As used herein, the terms “optional” or “optionally” mean that the subsequently described circumstance may or may not occur, so that the description includes instances where the circumstance occurs and instances where it does not. For example, the phrase “optionally substituted” means that a non-hydrogen substituent may or may not be present on a given atom, and, thus, the description includes structures wherein a non-hydrogen substituent is present and structures wherein a non-hydrogen substituent is not present.

Acetylene (ethyne) itself is a particularly attractive precursor for the various embodiments described herein, but other lower alkynes may also be employed, depending on the desired final polymer products. Similarly, aryl substituted alkynes may also be suitable. As will be described further below, anchored or tethered polyacetylenes are attractive products from the inventive methods.

Olefinic Precursors

Olefinic precursors may be used in tandem with the acetylenes, either employed as part of the feedstock mixtures, or in sequential processing of the product polymers. Suitable options for such precursors are those ring systems, particularly strained ring systems, which are useful for ROMP reactions. One such class of compounds in this regard is substituted or unsubstituted cyclooctatetraenes, including cyclooctatetraene itself. However, a polymer or polymer block derived from this material would be a polyacetylene, and this moiety is preferably derived in this invention from acetylene itself. Because cyclooctatetraene is made from acetylene, use of this latter precursor by an enyne reaction offers a more direct, efficient and economical synthesis. The ability to operate at the solid/gas interface for the surface confined polymerization of polyacetylene enables direct control over the pressure and temperature of the system.

When considering alternative olefinic precursors in the present methods, more preferred precursors may be those which, which when incorporated into polyacetylene polymers or copolymers, modify the electrical or physical character of the resulting polymer. One general class of such presursors are substituted annulenes and annulynes, for example [18]annulene-1,4;7,10;13,16-trisulfide. When co-polymerized with acetylene, this precursor can form a block co-polymer as shown here:

Substituted analogs of these trisulfides, as described below can also be used to provide corresponding substituted poly(thienylvinylene)-containing polymers or copolymers. For example, the 2,3,8,9,14,15-hexaoctyl derivative of [18]annulene-1,4;7,10;13,16-trisulfide is described in Horie, et al., “Poly(thienylvinylene) prepared by ring-opening metathesis polymerization: Performance as a donor in bulk heterojunction organic photovoltaic devices,” Polymer 51 (2010) 1541-1547, which is incorporated by reference herein for all purposes

As described above, suitable options for such olefinic or acetylenic precursors include ring systems, particularly strained ring systems, which are useful for ROMP reactions. Such cyclic olefins may be optionally substituted, optionally heteroatom-containing, mono-unsaturated, di-unsaturated, or poly-unsaturated C₅ to C₂₄ hydrocarbons that may be mono-, di-, or poly-cyclic. The cyclic olefin may generally be any strained or unstrained cyclic olefin, provided the cyclic olefin is able to participate in a ROMP reaction either individually or as part of a ROMP cyclic olefin composition. While certain unstrained cyclic olefins such as cyclohexene are generally understood to not undergo ROMP reactions by themselves, under appropriate circumstances, such unstrained cyclic olefins may nonetheless be ROMP active. For example, when present as a co-monomer in a ROMP composition, unstrained cyclic olefins may be ROMP active. Accordingly, as used herein and as would be appreciated by the skilled artisan, the term “unstrained cyclic olefin” is intended to refer to those unstrained cyclic olefins that may undergo a ROMP reaction under any conditions, or in any ROMP composition, provided the unstrained cyclic olefin is ROMP active.

In general, the cyclic olefin may be represented by the structure of formula (A)

wherein J, R^(A1), and R^(A2) are as follows:

R^(A1) and R^(A2) is selected independently from the group consisting of hydrogen, hydrocarbyl (e.g., C₁-C₂₀ alkyl, C₅-C₂₀ aryl, C₅-C₃₀ aralkyl, or C₅-C₃₀ alkaryl), substituted hydrocarbyl (e.g., substituted C₁-C₂₀ alkyl, C₅-C₂₀ aryl, C₅-C₃₀ aralkyl, or C₅-C₃₀ alkaryl), heteroatom-containing hydrocarbyl (e.g., C₁-C₂₀ heteroalkyl, C₅-C₂₀ heteroaryl, heteroatom-containing C₅-C₃₀ aralkyl, or heteroatom-containing C₅-C₃₀ alkaryl), and substituted heteroatom-containing hydrocarbyl (e.g., substituted C₁-C₂₀ heteroalkyl, C₅-C₂₀ heteroaryl, heteroatom-containing C₅-C₃₀ aralkyl, or heteroatom-containing C₅-C₃₀ alkaryl) and, if substituted hydrocarbyl or substituted heteroatom-containing hydrocarbyl, wherein the substituents may be functional groups (“Fn”) such as phosphonato, phosphoryl, phosphanyl, phosphino, sulfonato, C₁-C₂₀ alkylsulfanyl, C₅-C₂₀ arylsulfanyl, C₁-C₂₀ alkylsulfonyl, C₅-C₂₀ arylsulfonyl, C₁-C₂₀ alkylsulfinyl, C₅-C₂₀ arylsulfinyl, sulfonamido, amino, amido, imino, nitro, nitroso, hydroxyl, C₁-C₂₀ alkoxy, C₅-C₂₀ aryloxy, C₂-C₂₀ alkoxycarbonyl, C₅-C₂₀ aryloxycarbonyl, carboxyl, carboxylato, mercapto, formyl, C₁-C₂₀ thioester, cyano, cyanato, thiocyanato, isocyanate, thioisocyanate, carbamoyl, epoxy, styrenyl, silyl, silyloxy, silanyl, siloxazanyl, boronato, boryl, or halogen, or a metal-containing or metalloid-containing group (wherein the metal may be, for example, Sn or Ge). R^(A1) and R^(A2) may itself be one of the aforementioned groups, such that the Fn moiety is directly bound to the olefinic carbon atom indicated in the structure. In the latter case, however, the functional group will generally not be directly bound to the olefinic carbon through a heteroatom containing one or more lone pairs of electrons, e.g., an oxygen, sulfur, nitrogen, or phosphorus atom, or through an electron-rich metal or metalloid such as Ge, Sn, As, Sb, Se, Te, etc. With such functional groups, there will normally be an intervening linkage Z*, such that either or both of R^(A1) and R^(A2) then has the structure —(Z*)_(n)-Fn wherein n is 1, Fn is the functional group, and Z* is a hydrocarbylene linking group such as an alkylene, substituted alkylene, heteroalkylene, substituted heteroalkene, arylene, substituted arylene, heteroarylene, or substituted heteroarylene linkage.

J is a saturated or unsaturated hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, or substituted heteroatom-containing hydrocarbylene linkage, wherein when J is substituted hydrocarbylene or substituted heteroatom-containing hydrocarbylene, the substituents may include one or more —(Z*)_(n)-Fn groups, wherein n is zero or 1, and Fn and Z* are as defined previously. Additionally, two or more substituents attached to ring carbon (or other) atoms within J may be linked to form a bicyclic or polycyclic olefin. J will generally contain in the range of approximately 5 to 14 ring atoms, typically 5 to 8 ring atoms, for a monocyclic olefin, and, for bicyclic and polycyclic olefins, each ring will generally contain 4 to 8, typically 5 to 7, ring atoms.

Mono-unsaturated cyclic olefins encompassed by structure (A) may be represented by the structure (B)

wherein b is an integer generally although not necessarily in the range of 1 to 10, typically 1 to 5,

R^(A1) and R^(A2) are as defined above for structure (A), and R^(B1), R^(B2), R^(B3), R^(B4), R^(B5), and R^(B6) are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl and —(Z*)_(n)-Fn where n, Z* and Fn are as defined previously, and wherein if any of the R^(B1) through R^(B6) moieties is substituted hydrocarbyl or substituted heteroatom-containing hydrocarbyl, the substituents may include one or more —(Z*)_(n)-Fn groups. Accordingly, R^(B1), R^(B2), R^(B3), R^(B4), R^(B5), and R^(B6) may be, for example, hydrogen, hydroxyl, C₁-C₂₀ alkyl, C₅-C₂₀ aryl, C₁-C₂₀ alkoxy, C₅-C₂₀ aryloxy, C₂-C₂₀ alkoxycarbonyl, C₅-C₂₀ aryloxycarbonyl, amino, amido, nitro, etc.

Furthermore, any of the R^(B1), R^(B2), R^(B3), R^(B4), R^(B5), and R^(B6) moieties can be linked to any of the other R^(B1), R^(B2), R^(B3), R^(B4), R^(B5), and R^(B6) moieties to provide a substituted or unsubstituted alicyclic group containing 4 to 30 ring carbon atoms or a substituted or unsubstituted aryl group containing 6 to 18 ring carbon atoms or combinations thereof and the linkage may include heteroatoms or functional groups, e.g. the linkage may include without limitation an ether, ester, thioether, amino, alkylamino, imino, or anhydride moiety. The alicyclic group can be monocyclic, bicyclic, or polycyclic. When unsaturated the cyclic group can contain monounsaturation or multiunsaturation, with monounsaturated cyclic groups being preferred. When substituted, the rings contain monosubstitution or multisubstitution wherein the substituents are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, —(Z*)_(n)-Fn where n is zero or 1, Z* and Fn are as defined previously, and functional groups (Fn) provided above.

Examples of monounsaturated, monocyclic olefins encompassed by structure (B) include, without limitation, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, cycloundecene, cyclododecene, tricyclodecene, tetracyclodecene, octacyclodecene, and cycloeicosene, and substituted versions thereof such as 1-methylcyclopentene, 1-ethylcyclopentene, 1-isopropylcyclohexene, 1-chloropentene, 1-fluorocyclopentene, 4-methylcyclopentene, 4-methoxy-cyclopentene, 4-ethoxy-cyclopentene, cyclopent-3-ene-thiol, cyclopent-3-ene, 4-methylsulfanyl-cyclopentene, 3-methylcyclohexene, 1-methylcyclooctene, 1,5-dimethylcyclooctene, etc.

Monocyclic diene reactants encompassed by structure (A) may be generally represented by the structure (C)

wherein c and d are independently integers in the range of 1 to about 8, typically 2 to 4, preferably 2 (such that the reactant is a cyclooctadiene), R^(A1) and R^(A2) are as defined above for structure (A), and R^(C1), R^(C2), R^(C3), R^(C4), R^(C5), and R^(C6) are defined as for R^(B1) through R^(B6). In this case, it is preferred that R^(C3) and R^(C4) be non-hydrogen substituents, in which case the second olefinic moiety is tetrasubstituted. Examples of monocyclic diene reactants include, without limitation, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, 5-ethyl-1,3-cyclohexadiene, 1,3-cycloheptadiene, cyclohexadiene, 1,5-cyclooctadiene, 1,3-cyclooctadiene, and substituted analogs thereof. Triene reactants are analogous to the diene structure (C), and will generally contain at least one methylene linkage between any two olefinic segments. Bicyclic and polycyclic olefins encompassed by structure (A) may be generally represented by the structure (D)

wherein R^(A1) and R^(A2) are as defined above for structure (A), R^(D1), R^(D2), R^(D3), and R^(D4) are as defined for R^(B1) through R^(B6), e is an integer in the range of 1 to 8 (typically 2 to 4) f is generally 1 or 2; T is lower alkylene or alkenylene (generally substituted or unsubstituted methyl or ethyl), CHR^(G1), C(R^(G1))₂, O, S, N—R^(G1), P—R^(G1), O═P—R^(G1), Si(R^(G1))₂, B—R^(G1), or As—R^(G1) where R^(G1) is alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, alkaryl, aralkyl, or alkoxy. Furthermore, any of the R^(D1), R^(D2), R^(D3), and R^(D4) moieties can be linked to any of the other R^(D1), R^(D2), R^(D3), and R^(D4) moieties to provide a substituted or unsubstituted alicyclic group containing 4 to 30 ring carbon atoms or a substituted or unsubstituted aryl group containing 6 to 18 ring carbon atoms or combinations thereof and the linkage may include heteroatoms or functional groups, e.g. the linkage may include without limitation an ether, ester, thioether, amino, alkylamino, imino, or anhydride moiety. The cyclic group can be monocyclic, bicyclic, or polycyclic. When unsaturated the cyclic group can contain mono-unsaturation or multi-unsaturation, with mono-unsaturated cyclic groups being preferred. When substituted, the rings contain mono-substitution or multi-substitution wherein the substituents are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, —(Z*)_(n)-Fn where n is zero or 1, Z* and Fn are as defined previously, and functional groups (Fn) provided above.

Cyclic olefins encompassed by structure (D) are in the norbornene family. As used herein, norbornene means any compound that includes at least one norbornene or substituted norbornene moiety, including without limitation norbornene, substituted norbornene(s), norbornadiene, substituted norbornadiene(s), polycyclic norbornenes, and substituted polycyclic norbornene(s). Norbornenes within this group may be generally represented by the structure (E)

wherein R^(A1) and R^(A2) are as defined above for structure (A), T is as defined above for structure (D), R^(E1), R^(E2), R^(E3), R^(E4), R^(E5), R^(E6), R^(E7) and R^(E8) are as defined for R^(B1) through R^(B6), and “a” represents a single bond or a double bond, f is generally 1 or 2, “g” is an integer from 0 to 5, and when “a” is a double bond one of R^(E5), R^(E6) and one of R^(E7), R^(E8) is not present. Furthermore, any of the R^(E5), R^(E6), R^(E7), and R^(E8) moieties can be linked to any of the other R^(E5), R^(E6), R^(E7), and R^(E8) moieties to provide a substituted or unsubstituted alicyclic group containing 4 to 30 ring carbon atoms or a substituted or unsubstituted aryl group containing 6 to 18 ring carbon atoms or combinations thereof and the linkage may include heteroatoms or functional groups, e.g. the linkage may include without limitation an ether, ester, thioether, amino, alkylamino, imino, or anhydride moiety. The cyclic group can be monocyclic, bicyclic, or polycyclic. When unsaturated the cyclic group can contain monounsaturation or multiunsaturation, with monounsaturated cyclic groups being preferred. When substituted, the rings contain monosubstitution or multisubstitution wherein the substituents are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, —(Z*)_(n)-Fn where n is zero or 1, Z* and Fn are as defined previously, and functional groups (Fn) provided above.

More preferred cyclic olefins possessing at least one norbornene moiety have the structure (F):

wherein, R^(F1), R^(F2), R^(F3), and R^(F4), are as defined for R^(B1) through R^(B6), and “a” represents a single bond or a double bond, “g” is an integer from 0 to 5, and when “a” is a double bond one of R^(F1), R^(F2) and one of R^(F3), R^(F4) is not present.

Furthermore, any of the R^(F1), R^(F2), R^(F3), and R^(F4) moieties can be linked to any of the other R^(F1), R^(F2), R^(F3), and R^(F4) moieties to provide a substituted or unsubstituted alicyclic group containing 4 to 30 ring carbon atoms or a substituted or unsubstituted aryl group containing 6 to 18 ring carbon atoms or combinations thereof and the linkage may include heteroatoms or functional groups, e.g. the linkage may include without limitation an ether, ester, thioether, amino, alkylamino, imino, or anhydride moiety. The alicyclic group can be monocyclic, bicyclic, or polycyclic. When unsaturated the cyclic group can contain monounsaturation or multiunsaturation, with monounsaturated cyclic groups being preferred. When substituted, the rings contain monosubstitution or multisubstitution wherein the substituents are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, —(Z*)_(n)-Fn where n is zero or 1, Z* and Fn are as defined previously, and functional groups (Fn) provided above.

One route for the preparation of hydrocarbyl substituted and functionally substituted norbornenes employs the Diels-Alder cycloaddition reaction in which cyclopentadiene or substituted cyclopentadiene is reacted with a suitable dienophile at elevated temperatures to form the substituted norbornene adduct generally shown by the following reaction Scheme 4:

wherein R^(F1) to R^(F4) are as previously defined for structure (F).

Other norbornene adducts can be prepared by the thermal pyrolysis of dicyclopentadiene in the presence of a suitable dienophile. The reaction proceeds by the initial pyrolysis of dicyclopentadiene to cyclopentadiene followed by the Diels-Alder cycloaddition of cyclopentadiene and the dienophile to give the adduct shown below in Scheme 5:

wherein “g” is an integer from 0 to 5, and R^(F1) to R^(F4) are as previously defined for structure (F).

Norbornadiene and higher Diels-Alder adducts thereof similarly can be prepared by the thermal reaction of cyclopentadiene and dicyclopentadiene in the presence of an acetylenic reactant as shown below in Scheme 6:

herein “g” is an integer from 0 to 5, R^(F1) and R^(F4) are as previously defined for structure (F) Examples of bicyclic and polycyclic olefins thus include, without limitation, dicyclopentadiene (DCPD); trimer and other higher order oligomers of cyclopentadiene including without limitation tricyclopentadiene (cyclopentadiene trimer), cyclopentadiene tetramer, and cyclopentadiene pentamer; ethylidenenorbornene; dicyclohexadiene; norbornene; 5-methyl-2-norbornene; 5-ethyl-2-norbornene; 5-isobutyl-2-norbornene; 5,6-dimethyl-2-norbornene; 5-phenylnorbornene; 5-benzylnorbornene; 5-acetylnorbornene; 5-methoxycarbonylnorbornene; 5-ethyoxycarbonyl-1-norbornene; 5-methyl-5-methoxy-carbonylnorbornene; 5-cyanonorbornene; 5,5,6-trimethyl-2-norbornene; cyclo-hexenylnorbornene; endo, exo-5,6-dimethoxynorbornene; endo, endo-5,6-dimethoxynorbornene; endo, exo-5,6-dimethoxycarbonylnorbornene; endo,endo-5,6-dimethoxycarbonylnorbornene; 2,3-dimethoxynorbornene; norbornadiene; tricycloundecene; tetracyclododecene; 8-methyltetracyclododecene; 8-ethyltetracyclododecene; 8-methoxycarbonyltetracyclododecene; 8-methyl-8-tetracyclododecene; 8-cyanotetracyclododecene; pentacyclopentadecene; pentacyclohexadecene; and the like, and their structural isomers, stereoisomers, and mixtures thereof. Additional examples of bicyclic and polycyclic olefins include, without limitation, C₂-C₁₂ hydrocarbyl substituted norbornenes such as 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-octyl-2-norbornene, 5-decyl-2-norbornene, 5-dodecyl-2-norbornene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-isopropenyl-2-norbornene, 5-propenyl-2-norbornene, and 5-butenyl-2-norbornene, and the like.

Preferred cyclic olefins include C₅ to C₂₄ unsaturated hydrocarbons. Also preferred are C₅ to C₂₄ cyclic hydrocarbons that contain one or more (typically 2 to 12) heteroatoms such as O, N, S, or P. For example, crown ether cyclic olefins may include numerous O heteroatoms throughout the cycle, and these are within the scope of the invention. In addition, preferred cyclic olefins are C₅ to C₂₄ hydrocarbons that contain one or more (typically 2 or 3) olefins. For example, the cyclic olefin may be mono-, di-, or tri-unsaturated. Examples of cyclic olefins include without limitation cyclooctene, cyclododecene, and (c,t,t)-1,5,9-cyclododecatriene.

The cyclic olefins may also comprise multiple (typically 2 or 3) rings. For example, the cyclic olefin may be mono-, di-, or tri-cyclic. When the cyclic olefin comprises more than one ring, the rings may or may not be fused. Preferred examples of cyclic olefins that comprise multiple rings include norbornene, dicyclopentadiene, tricyclopentadiene, and 5-ethylidene-2-norbornene.

The cyclic olefin may also be substituted, for example, a C₅ to C₂₄ cyclic hydrocarbon wherein one or more (typically 2, 3, 4, or 5) of the hydrogens are replaced with non-hydrogen substituents. Suitable non-hydrogen substituents may be chosen from the substituents described hereinabove. For example, functionalized cyclic olefins, i.e., C₅ to C₂₄ cyclic hydrocarbons wherein one or more (typically 2, 3, 4, or 5) of the hydrogens are replaced with functional groups, are within the scope of the invention. Suitable functional groups may be chosen from the functional groups described hereinabove. For example, a cyclic olefin functionalized with an alcohol group may be used to prepare a telechelic polymer comprising pendent alcohol groups. Functional groups on the cyclic olefin may be protected in cases where the functional group interferes with the metathesis catalyst, and any of the protecting groups commonly used in the art may be employed. Acceptable protecting groups may be found, for example, in Greene et al., Protective Groups in Organic Synthesis, 3rd Ed. (New York: Wiley, 1999). Examples of functionalized cyclic olefins include without limitation 2-hydroxymethyl-5-norbornene, 2-[(2-hydroxyethyl)carboxylate]-5-norbornene, cydecanol, 5-n-hexyl-2-norbornene, 5-n-butyl-2-norbornene.

Cyclic olefins incorporating any combination of the abovementioned features (i.e., heteroatoms, substituents, multiple olefins, multiple rings) are suitable for the methods disclosed herein. Additionally, cyclic olefins incorporating any combination of the abovementioned features (i.e., heteroatoms, substituents, multiple olefins, multiple rings) are suitable for the invention disclosed herein.

The cyclic olefins useful in the methods disclosed herein may be strained or unstrained. It will be appreciated that the amount of ring strain varies for each cyclic olefin compound, and depends upon a number of factors including the size of the ring, the presence and identity of substituents, and the presence of multiple rings. Ring strain is one factor in determining the reactivity of a molecule towards ring-opening olefin metathesis reactions. Highly strained cyclic olefins, such as certain bicyclic compounds, readily undergo ring opening reactions with olefin metathesis catalysts. Less strained cyclic olefins, such as certain unsubstituted hydrocarbon monocyclic olefins, are generally less reactive. In some cases, ring opening reactions of relatively unstrained (and therefore relatively unreactive) cyclic olefins may become possible when performed in the presence of the olefinic compounds disclosed herein. Additionally, cyclic olefins useful in the invention disclosed herein may be strained or unstrained.

A plurality of cyclic olefins may be used with the present invention to prepare metathesis polymers. For example, two cyclic olefins selected from the cyclic olefins described hereinabove may be employed in order to form metathesis products that incorporate both cyclic olefins. Where two or more cyclic olefins are used, one example of a second cyclic olefin is a cyclic alkenol, i.e., a C₅-C₂₄ cyclic hydrocarbon wherein at least one of the hydrogen substituents is replaced with an alcohol or protected alcohol moiety to yield a functionalized cyclic olefin.

The use of a plurality of cyclic olefins, and in particular when at least one of the cyclic olefins is functionalized, allows for further control over the positioning of functional groups within the products. For example, the density of cross-linking points can be controlled in polymers and macromonomers prepared using the methods disclosed herein. Control over the quantity and density of substituents and functional groups also allows for control over the physical properties (e.g., melting point, tensile strength, glass transition temperature, etc.) of the products. Control over these and other properties is possible for reactions using only a single cyclic olefin, but it will be appreciated that the use of a plurality of cyclic olefins further enhances the range of possible metathesis products and polymers formed.

More preferred cyclic olefins include dicyclopentadiene; tricyclopentadiene; dicyclohexadiene; norbornene; 5-methyl-2-norbornene; 5-ethyl-2-norbornene; 5-isobutyl-2-norbornene; 5,6-dimethyl-2-norbornene; 5-phenylnorbornene; 5-benzylnorbornene; 5-acetylnorbornene; 5-methoxycarbonylnorbornene; 5-ethoxycarbonyl-1-norbornene; 5-methyl-5-methoxy-carbonylnorbornene; 5-cyanonorbornene; 5,5,6-trimethyl-2-norbornene; cyclo-hexenylnorbornene; endo, exo-5,6-dimethoxynorbornene; endo, endo-5,6-dimethoxynorbornene; endo, exo-5-6-dimethoxycarbonylnorbornene; endo, endo-5,6-dimethoxycarbonylnorbornene; 2,3-dimethoxynorbornene; norbornadiene; tricycloundecene; tetracyclododecene; 8-methyltetracyclododecene; 8-ethyl-tetracyclododecene; 8-methoxycarbonyltetracyclododecene; 8-methyl-8-tetracyclo-dodecene; 8-cyanotetracyclododecene; pentacyclopentadecene; pentacyclohexadecene; higher order oligomers of cyclopentadiene such as cyclopentadiene tetramer, cyclopentadiene pentamer, and the like; and C₂-C₁₂ hydrocarbyl substituted norbornenes such as 5-butyl-2-norbornene; 5-hexyl-2-norbornene; 5-octyl-2-norbornene; 5-decyl-2-norbornene; 5-dodecyl-2-norbornene; 5-vinyl-2-norbornene; 5-ethylidene-2-norbornene; 5-isopropenyl-2-norbornene; 5-propenyl-2-norbornene; and 5-butenyl-2-norbornene, and the like. Even more preferred cyclic olefins include dicyclopentadiene, tricyclopentadiene, and higher order oligomers of cyclopentadiene, such as cyclopentadiene tetramer, cyclopentadiene pentamer, and the like, tetracyclododecene, norbornene, and C₂-C₁₂ hydrocarbyl substituted norbornenes, such as 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-octyl-2-norbornene, 5-decyl-2-norbornene, 5-dodecyl-2-norbornene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-isopropenyl-2-norbornene, 5-propenyl-2-norbornene, 5-butenyl-2-norbornene, and the like.

Tethered Polymer Arrays

To this point, the methods have been described in terms of growing product polymer(s), without regard for orientation or attachment of the resulting polymers. While various embodiments do provide that the methods may be used to form loose, unattached, or “free-standing” polymers, the methods also may be used to grow polymers which are tethered or attached to a substrate surface, either through single points or attachment at one end, or through multiple “engagement points” along the length of the polymer; i.e., where the polymer is bound to a substrate surface. In either case, the resulting polymers may be attached to the substrate surface by covalent bonding, hydrogen bonding, ionic bonding, physisorption, pi-pi interaction, Van der Waals forces, or a combination thereof. These points of attachments may be via linkages comprising functional groups such as amino, carbene, carboxylate, catecholate, a dithiocarbamate, dithioic acid, hydroxy, hydroxyamic acid, isocyanato, nitrite, phosphate, phosphonate, a silane or silicate, or thiol groups. One of ordinary skill in the art would be familiar with these and other chemical groups that are able to form an attachment to the surface.

In describing such polymers which are tethered or attached to a substrate surface at one end, it is useful to describe an individual polymer as having proximal and distal ends, in which the proximal end(s) is/are those ends closest or tethered to the surface, and the distal end(s) is/are those ends of the polymers which stand away from the substrate surface. While not intending to be bound by the correctness or incorrectness of any particular theory, it may be useful to view the growth of such a polymer, tethered at its proximal end to the substrate surface, as resulting from a metathesis reaction in which the metathesis catalyst remains bonded to and reacts with gaseous or vapor precursor at the “living,” distal end of the polymer, for example by a carbene linkage. As the methods proceed, the polymer product grows, either individually or as a plurality of individual polymer strands via the associated metathesis reactions, so as to extend away from the surface.

Such a tethered structure may be formed, for example, by pre-reacting a second, end-functionalized olefinic or acetylenic precursor with a surface, under conditions sufficient to attach the end-functionalized olefinic or acetylenic precursor to the surface. The term “second, end-functionalized” is intended to connote that this precursor may be the same or different from the feedstock precursor used in the metathesis reaction(s), in terms of the nature of the unsaturated moiety, and that it contains a functional group (as described above) useful for bonding to the substrate. Once in place, for example as a monolayer on the substrate, the second, end-functionalized precursor is modified to incorporate the catalyst complex. This may be accomplished by reacting the second, end-functionalized precursor, now tethered, with a suitable metathesis catalyst, with or without solvent, to form the necessary initiator for the subsequent metathesis reaction(s). Note that if solvent is used during the generation of this initiator, it is to be removed—by vacuum, heat, or both—prior to operating the inventive methods. Once the metathesis catalyst is tethered to the surface, via the second, end-functionalized precursor, the feedstock is introduced to initiate the polymerization of a linear chain with the catalyst at the terminus. The growing polymer chain terminates at a double bonded between a carbon and a metal center of the catalyst. Accordingly, the catalyst remains at the terminal, distal end of the growing polymer chain and the growth occurs by adding additional feedstock precursors to the terminal, distal end of the polymer chain.

These concepts are illustrated in FIG. 1.

Another way of generating this initiator monolayer is to use a metathesis catalyst, which already contains the functional group necessary for attachment to the surface. In such embodiments, the catalyst may be deposited from a solution, where the solution solvent is removed before the conditions associated with the direct vapor/solid phase or direct gas/solid phase polymerization are employed.

The terms “surface,” “substrate” and “substrate material” as used herein, are intended to generally mean any material from which the tethered polymers grow, or where the catalytic initiators are contacted with, applied to, or bonded to. These terms may be viewed in terms of planar or substantially planar (e.g., curved or undulating) surfaces, but also include particulate (e.g., spherical or oblate) or elongated surfaces (e.g., cylindrically shaped tubes or fibers), having at least one dimension in the nanometer range (e.g., in a range from about 1 nm to about 1000 nm), micron range (e.g., in a range from about 1 micron to about 1000 micron), or larger (e.g., in a range from about 1 cm and above), or a combination thereof.

In those embodiments where the polymer product is “grown” from a surface, the surface may comprise a synthetic, semi-synthetic, or naturally occurring materials, which may be organic or inorganic, e.g., polymeric, ceramic, or metallic. Without limitation, such materials include metals, metal oxides, polymers, glass, ceramics, filaments, fibers, rovings, mats, weaves, fabrics, knitted material, cloth or other known structures, glass fibers and fabrics, carbon fibers and fabrics, aramid fibers and fabrics, polyolefin or other polymer fibers or fabrics, any material possessing a surface containing hydroxyl functional groups, silicas, silicates, aluminas, aluminum oxides, silica-aluminas, aluminosilicates, zeolites, titanias, titanium dioxide, magnetite, magnesium oxides, boron oxides, clays, zirconias, zirconium dioxide, carbon, titanium oxides, silicon oxides, iron oxides, indium tin oxide (ITO), fluorine tin oxide (PTO), gallium arsenide oxides, copper oxides, zirconium oxides, zinc oxides, yttrium oxides, cellulose, cellulosic polymers amylose, amylosic polymers, or a combination thereof. Preferred exemplary, non-limiting surfaces include those comprising Au, Ag, Cu, Pd, Pt, GaAs, oxides of Al, Cu, Fe, Si, Ti, Y, Zn, Zr, or mixed oxides such as silicate glasses, indium-tin-oxide (ITO), or fluorine tin oxide (FTO).

It should be apparent that the combination of substrates and potential polymer compositions described herein can yield any combination of conducting/semiconducting surface and conducting/semiconducting polymer. Where appropriate, it is preferred that the tethering moiety is either non-insulative or can allow electron hopping. It should also be apparent that the initiator moieties may be patterned on the relevant surface, for example, by use of photomasking technology, by selective deposition of the catalyst, or both.

One of the many attractive features of the methods described herein is the ability of these methods to provide patterned arrays of oriented polymer strands or arrays. The active or final polymer chains may be aligned with one another or, depending on the length of the polymer strands, may form disarrayed mats. When aligned, each active polymer extends away from the surface. In certain embodiments, the individual polymer strands may be described as substantially parallel to one another. Assuming the polymer chains are substantially linear, this measure of alignment can be described in terms imaginary end-to-end vector which can be envisioned to extend between the proximal and distal ends of the individual polymer chains. Alignment is achieved when these lines are parallel or substantially parallel to one another. For instance, each line can have an angle relative to the surface (θ_(x)), and the average of the individual lines can be used to define an average angle between each line and the first surface (θ,_(avg)). The alignment of the polymers can be described, using these terms, by the portion of the individual polymers (e.g., more than 50%, 75%, or even 90%) whose angle relative to the surface (θ_(x)) that is within some measure (e.g., +/−40°, 20°, 10°, or 5°) of the angle (θ,_(avg)). Additionally or alternately, the angle (θ,_(avg)) itself can be used to describe the orientation of the polymer array with respect to the surface. The term “substantially parallel” refers to a condition where the angles of the individual polymer strands are collectively ±20° of angle, θ,_(avg). In other embodiments, the polymer arrays are normal to the surface of the substrate, where normal is defined as when θ,_(avg) is within ±20° of 90°. The methods described in this disclosure are especially useful because the 2-dimensional confinement of the catalysts enables the alignment of polymers to these levels. This is especially attractive for those polymers having properties useful for optical or electronic devices, when tethered to one or more electrode surfaces.

The use of self-assembled monolayers allows the first anchoring groups to be densely packed on the optionally patterned surface. Growing the polymer chains on densely packed first anchoring groups keeps the polymer chains densely packed. Additionally, the consistency in the rate at which each chain grows effectively causes the polymer chains to be formed one layer at a time. The combination of the dense packing and forming the polymer chains in layers causes the pattern in which the first anchoring groups 16 are arranged on the surface to be retained through the polymer chains as discussed above.

Performing direct gas/solid phase polymerization reactions may provide even further alignment of the polymer chains. For instance, the rate of diffusion of the catalyst in is significantly lower at a vapor/solid interface (even where localized condensation of the feedstock precursor result in a localized liquid/solid interface) than in solution. Diffusion is even lower at a direct gas/solid phase interface (where such localized condensation of the feedstock precursor is much less likely, if not impossible). This reduced rate of diffusion reduces the opportunity for the polymer chains to change directions during growth. As a result, performing the ring-opening metathesis polymerizations using a direct gas/solid phase interface can further enhance of the alignment of the polymer chains.

Transition Metal-Based Metathesis Catalysts

Transition metal-based metathesis catalysts suitable for use in alkene or alkyne metathesis chemistry include those alkylidene or alkylidyne complexes (or precursors which may generated organometallic alkylidene or alkylidyne complexes) comprising Mo, Pd, Ru, Ta, Ti, or W. Non-limiting examples include systems based on structures such as:

While such catalyst systems are known in solvent based metatheses contexts, to the inventors' knowledge, none of these have been applied to direct vapor solid phase or direct gas/solid phase reactions, nor are they known to be useful in this context. Yet these, and derivatives thereof, may be suitable for use in the reactions described herein.

Organometallic complexes based on Group 8 metals, especially osmium and ruthenium, especially those of ruthenium containing N-heterocyclic carbene ligands, are especially useful in the embodiments described herein. In particular, the various generations of complexes known as Grubbs' catalyst, are preferred. These catalysts have been described, inter alia, in U.S. Pat. Nos. 5,312,940; 5,342,909; 5,750,815; 5,831,108; 5,917,071; 5,969,170; 5,977,393; 6,048,993; 6,111,121; 6,153,778; 6,211,391; 6,284,852; 6,313,332; 6,426,419; 6,486,279; 6,504,041; 6,515,084; 6,624,265; 6,759,537; 6,806,325; 6,818,586; 7,102,047; 7,288,666; 7,329,758; and 7,750,172 and U.S. Patent Application Publ. Nos. 2001/0039360; 2002/0013473; 2002/0022733; 2002/0055598; 2002/0177710; 2003/0069374; 2003/0181609; 2005/0113590; 2006/0241317; 2009/0012248; 2009/0012254; and 2011/0124868, each of which is incorporated by reference for its teaching of catalyst and catalyst precursor structure. The term “Grubbs-type catalyst” is intended to embrace one or more of the structures described below (including First and Second Generation Grubbs-Type catalysts and Grubbs-Hoveyda catalysts), and the term “Grubbs-type ruthenium catalysts” likewise connotes those Grubbs-type catalyst structures where M is Ru.

In certain embodiments of the present invention, the transition metal-based metathesis catalyst complex is preferably a Group 8 transition metal complex having the structure of formula (I)

in which:

M is a Group 8 transition metal;

L¹, L², and L³ are neutral electron donor ligands;

n is 0 or 1, such that L³ may or may not be present;

m is 0, 1, or 2;

k is 0 or 1;

X¹ and X² are anionic ligands; and

R¹ and R² are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups,

wherein any two or more of X¹, X², L¹, L², L³, R¹, and R² can be taken together to form one or more cyclic groups.

Additionally, in formula (I), one or both of R¹ and R² may have the structure —(W)_(n)—U⁺V⁻, in which W is selected from hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, or substituted heteroatom-containing hydrocarbylene; U is a positively charged Group 15 or Group 16 element substituted with hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; V is a negatively charged counterion; and n is zero or 1. Furthermore, R¹ and R² may be taken together to form an indenylidene moiety.

Preferred catalysts contain Ru or Os as the Group 8 transition metal, with Ru particularly preferred.

Numerous embodiments of the catalysts useful in the reactions disclosed herein are described in more detail infra. For the sake of convenience, the catalysts are described in groups, but it should be emphasized that these groups are not meant to be limiting in any way. That is, any of the catalysts useful in the invention may fit the description of more than one of the groups described herein.

A first group of catalysts, then, are commonly referred to as First Generation Grubbs-type catalysts, and have the structure of formula (I). For the first group of catalysts, M is a Group 8 transition metal, m is 0, 1, or 2, and n, X¹, X², L¹, L², L³, R¹, and R² are described as follows. For the first group of catalysts, n is 0, and L¹ and L² are independently selected from phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, arsine, stibine, ether, (including cyclic ethers), amine, amide, imine, sulfoxide, carboxyl, nitrosyl, pyridine, substituted pyridine, imidazole, substituted imidazole, pyrazine, substituted pyrazine and thioether. Exemplary ligands are trisubstituted phosphines. Preferred trisubstituted phosphines are of the formula PR^(H1)R^(H2)R^(H3), where R^(H1), R^(H2), and R^(H3) are each independently substituted or unsubstituted aryl or C₁-C₁₀ alkyl, particularly primary alkyl, secondary alkyl, or cycloalkyl. In the most preferred, L¹ and L² are independently selected from the group consisting of trimethylphosphine (PMe₃), triethylphosphine (PEt₃), tri-n-butylphosphine (PBu₃), tri(ortho-tolyl)phosphine (P-o-tolyl₃), tri-tert-butylphosphine (P-tert-Bu₃), tricyclopentylphosphine (PCyclopentyl₃), tricyclohexylphosphine (PCy₃), triisopropylphosphine (P-i-Pr₃), trioctylphosphine (POct₃), triisobutylphosphine, (P-i-Bu₃), triphenylphosphine (PPh₃), tri(pentafluorophenyl)phosphine (P(C₆F₅)₃), methyldiphenylphosphine (PMePh₂), dimethylphenylphosphine (PMe₂Ph), and diethylphenylphosphine (PEt₂Ph). Alternatively, L¹ and L² may be independently selected from phosphabicycloalkane (e.g. monosubstituted 9-phosphabicyclo-[3.3.1]nonane, or monosubstituted 9-phosphabicyclo[4.2.1]nonane] such as cyclohexylphoban, isopropylphoban, ethylphoban, methylphoban, butylphoban, pentylphoban and the like).

X¹ and X² are anionic ligands, and may be the same or different, or are linked together to form a cyclic group, typically although not necessarily a five- to eight-membered ring. In preferred embodiments, X¹ and X² are each independently hydrogen, halide, or one of the following groups: C₁-C₂₀ alkyl, C₅-C₂₄ aryl, C₁-C₂₀ alkoxy, C₅-C₂₄ aryloxy, C₂-C₂₀ alkoxycarbonyl, C₆-C₂₄ aryloxycarbonyl, C₂-C₂₄ acyl, C₂-C₂₄ acyloxy, C₁-C₂₀ alkylsulfonato, C₅-C₂₄ arylsulfonato, C₁-C₂₀ alkylsulfanyl, C₅-C₂₄ arylsulfanyl, C₁-C₂₀ alkylsulfinyl, NO₃, —N═C═O, —N═C═S, or C₅-C₂₄ arylsulfinyl. Optionally, X¹ and X² may be substituted with one or more moieties selected from C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy, C₅-C₂₄ aryl, and halide, which may, in turn, with the exception of halide, be further substituted with one or more groups selected from halide, C₁-C₆ alkyl, C₁-C₆ alkoxy, and phenyl. In more preferred embodiments, X¹ and X² are halide, benzoate, C₂-C₆ acyl, C₂-C₆ alkoxycarbonyl, C₁-C₆ alkyl, phenoxy, C₁-C₆ alkoxy, C₁-C₆ alkylsulfanyl, aryl, or C₁-C₆ alkylsulfonyl. In even more preferred embodiments, X¹ and X² are each halide, CF₃CO₂, CH₃CO₂, CFH₂CO₂, (CH₃)₃CO, (CF₃)₂(CH₃)CO, (CF₃)(CH₃)₂CO, PhO, MeO, EtO, tosylate, mesylate, or trifluoromethane-sulfonate. In the most preferred embodiments, X¹ and X² are each chloride.

R¹ and R² are independently selected from hydrogen, hydrocarbyl (e.g., C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, C₆-C₂₄ aralkyl, etc.), substituted hydrocarbyl (e.g., substituted C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, C₆-C₂₄ aralkyl, etc.), heteroatom-containing hydrocarbyl (e.g., heteroatom-containing C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, C₆-C₂₄ aralkyl, etc.), and substituted heteroatom-containing hydrocarbyl (e.g., substituted heteroatom-containing C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, C₆-C₂₄ aralkyl, etc.), and functional groups. R¹ and R² may also be linked to form a cyclic group, which may be aliphatic or aromatic, and may contain substituents, heteroatoms, or both. Generally, such a cyclic group will contain 4 to 12, preferably 5, 6, 7, or 8 ring atoms.

In preferred catalysts, R¹ is hydrogen and R² is selected from C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, and C₅-C₂₄ aryl, more preferably C₁-C₆ alkyl, C₂-C₆ alkenyl, and C₅-C₁₄ aryl. Still more preferably, R² is phenyl, vinyl, methyl, isopropyl, or t-butyl, optionally substituted with one or more moieties selected from C₁-C₆ alkyl, C₁-C₆ alkoxy, phenyl, and a functional group Fn as defined earlier herein. Most preferably, R² is phenyl or vinyl substituted with one or more moieties selected from methyl, ethyl, chloro, bromo, iodo, fluoro, nitro, dimethylamino, methyl, methoxy, and phenyl. Optimally, R² is phenyl or —CH═C(CH₃)₂.

Any two or more (typically two, three, or four) of X¹, X², L¹, L², L³, R¹, and R² can be taken together to form a cyclic group, including bidentate or multidentate ligands, as disclosed, for example, in U.S. Pat. No. 5,312,940, the disclosure of which is incorporated herein by reference. When any of X¹, X², L¹, L², L³, R¹, and R² are linked to form cyclic groups, those cyclic groups may contain 4 to 12, preferably 4, 5, 6, 7 or 8 atoms, or may comprise two or three of such rings, which may be either fused or linked. The cyclic groups may be aliphatic or aromatic, and may be heteroatom-containing or substituted. The cyclic group may, in some cases, form a bidentate ligand or a tridentate ligand. Examples of bidentate ligands include, but are not limited to, bisphosphines, dialkoxides, alkyldiketonates, and aryldiketonates.

A second group of catalysts, commonly referred to as Second Generation Grubbs-type catalysts, have the structure of formula (I), wherein L¹ is a carbene ligand having the structure of formula (II)

such that the complex may have the structure of formula (III)

wherein M, m, n, X¹, X², L², L³, R¹, and R² are as defined for the first group of catalysts, and the remaining substituents are as follows;

X and Y are heteroatoms typically selected from N, O, S, and P. Since O and S are divalent, p is necessarily zero when X is O or S, q is necessarily zero when Y is O or S, and k is zero or 1. However, when X is N or P, then p is 1, and when Y is N or P, then q is 1. In a preferred embodiment, both X and Y are N;

Q¹, Q², Q³, and Q⁴ are linkers, e.g., hydrocarbylene (including substituted hydrocarbylene, heteroatom-containing hydrocarbylene, and substituted heteroatom-containing hydrocarbylene, such as substituted, heteroatom-containing alkylene, or both) or —(CO)—, and w, x, y, and z are independently zero or 1, meaning that each linker is optional. Preferably, w, x, y, and z are all zero. Further, two or more substituents on adjacent atoms within Q¹, Q², Q³, and Q⁴ may be linked to form an additional cyclic group; and

R³, R^(3A), R⁴, and R^(4A) are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom-containing hydrocarbyl. In addition, X and Y may be independently selected from carbon and one of the heteroatoms mentioned above. Also, L² and L³ may be taken together to form a single bindentate electron-donating heterocyclic ligand. Furthermore, R¹ and R² may be taken together to form an indenylidene moiety. Moreover, X¹, X², L², L³, X and Y may be further coordinated to boron or to a carboxylate.

In addition, any two or more of X¹, X², L¹, L², L³, R¹, R², R³, R^(3A), R⁴, R^(4A), Q¹, Q², Q³, and Q⁴ can be taken together to form a cyclic group. Any two or more of X¹, X², L¹, L², L³, R¹, R², R³, R^(3A), R⁴, and R^(4A) can also be taken to be -A-Fn, wherein “A” is a divalent hydrocarbon moiety selected from alkylene and arylalkylene, wherein the alkyl portion of the alkylene and arylalkylene groups can be linear or branched, saturated or unsaturated, cyclic or acyclic, and substituted or unsubstituted, wherein the aryl portion of the of arylalkylene can be substituted or unsubstituted, and wherein hetero atoms and functional groups may be present in either the aryl or the alkyl portions of the alkylene and arylalkylene groups, and Fn is a functional group, or together to form a cyclic group.

Preferably, R^(3A) and R^(4A) are linked to form a cyclic group so that the carbene ligand has the structure of formula (IV)

wherein R³ and R⁴ are as defined for the second group of catalysts above, with preferably at least one of R³ and R⁴, and more preferably both R³ and R⁴, being alicyclic or aromatic of one to about five rings, and optionally containing one or more heteroatoms, or substituents, or both. Q is a linker, typically a hydrocarbylene linker, including substituted hydrocarbylene, heteroatom-containing hydrocarbylene, and substituted heteroatom-containing hydrocarbylene linkers, wherein two or more substituents on adjacent atoms within Q may also be linked to form an additional cyclic structure, which may be similarly substituted to provide a fused polycyclic structure of two to about five cyclic groups. Q is often, although not necessarily, a two-atom linkage or a three-atom linkage.

Examples of N-heterocyclic carbene (NHC) ligands and acyclic diaminocarbene ligands suitable as L¹ thus include, but are not limited to, the following where DIPP or DiPP is diisopropylphenyl and Mes is 2,4,6-trimethylphenyl:

Additional examples of N-heterocyclic carbene (NHC) ligands and acyclic diaminocarbene ligands suitable as L¹ thus include, but are not limited to the following:

wherein R^(W1), R^(W2), R^(W3), R^(W4) are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, or heteroatom containing hydrocarbyl, and where one or both of R^(W3) and R^(W4) may be in independently selected from halogen, nitro, amido, carboxyl, alkoxy, aryloxy, sulfonyl, carbonyl, thio, or nitroso groups.

Additional examples of N-heterocyclic carbene (NHC) ligands suitable as L¹ are further described in U.S. Pat. Nos. 7,378,528; 7,652,145; 7,294,717; 6,787,620; 6,635,768; and 6,552,139 the contents of each are incorporated herein by reference.

When M is ruthenium, then, the preferred complexes have the structure of formula (V)

In a more preferred embodiment, Q is a two-atom linkage having the structure —CR¹¹R¹²—CR¹³R¹⁴— or —CR¹¹═CR¹³—, preferably —CR¹¹R¹²—CR¹³R¹⁴—, wherein R¹¹, R¹², R¹³, and R¹⁴ are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups. Examples of functional groups here include without limitation carboxyl, C₁-C₂₀ alkoxy, C₅-C₂₄ aryloxy, C₂-C₂₀ alkoxycarbonyl, C₅-C₂₄ alkoxycarbonyl, C₂-C₂₄ acyloxy, C₁-C₂₀ alkylthio, C₅-C₂₄ arylthio, C₁-C₂₀ alkylsulfonyl, and C₁-C₂₀ alkylsulfinyl, optionally substituted with one or more moieties selected from C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy, C₅-C₁₄ aryl, hydroxyl, sulfhydryl, formyl, and halide. R¹¹, R¹², R¹³, and R¹⁴ are preferably independently selected from hydrogen, C₁-C₁₂ alkyl, substituted C₁-C₁₂ alkyl, C₁-C₁₂ heteroalkyl, substituted C₁-C₁₂ heteroalkyl, phenyl, and substituted phenyl. Alternatively, any two of R¹¹, R¹², R¹³, and R¹⁴ may be linked together to form a substituted or unsubstituted, saturated or unsaturated ring structure, e.g., a C₄-C₁₂ alicyclic group or a C₅ or C₆ aryl group, which may itself be substituted, e.g., with linked or fused alicyclic or aromatic groups, or with other substituents. In one further aspect, any one or more of R¹¹, R¹², R¹³, and R¹⁴ comprises one or more of the linkers. Additionally, R³ and R⁴ may be unsubstituted phenyl or phenyl substituted with one or more substituents selected from C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀ heteroalkyl, C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, C₅-C₂₄ heteroaryl, C₆-C₂₄ aralkyl, C₆-C₂₄ alkaryl, or halide. Furthermore, X¹ and X² may be halogen.

When R³ and R⁴ are aromatic, they are typically although not necessarily composed of one or two aromatic rings, which may or may not be substituted, e.g., R³ and R⁴ may be phenyl, substituted phenyl, biphenyl, substituted biphenyl, or the like. In one preferred embodiment, R³ and R⁴ are the same and are each unsubstituted phenyl or phenyl substituted with up to three substituents selected from C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀ heteroalkyl, C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, C₅-C₂₄ heteroaryl, C₆-C₂₄ aralkyl, C₆-C₂₄ alkaryl, or halide. Preferably, any substituents present are hydrogen, C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy, C₅-C₁₄ aryl, substituted C₅-C₁₄ aryl, or halide. As an example, R³ and R⁴ are mesityl (i.e. Mes as defined herein).

In a third group of catalysts having the structure of formula (I), M, m, n, X¹, X², R¹, and R² are as defined for the first group of catalysts, L¹ is a strongly coordinating neutral electron donor ligand such as any of those described for the first and second group of catalysts, and L² and L³ are weakly coordinating neutral electron donor ligands in the form of optionally substituted heterocyclic groups. Again, n is zero or 1, such that L³ may or may not be present. Generally, in the third group of catalysts, L² and L³ are optionally substituted five- or six-membered monocyclic groups containing 1 to 4, preferably 1 to 3, most preferably 1 to 2 heteroatoms, or are optionally substituted bicyclic or polycyclic structures composed of 2 to 5 such five- or six-membered monocyclic groups. If the heterocyclic group is substituted, it should not be substituted on a coordinating heteroatom, and any one cyclic moiety within a heterocyclic group will generally not be substituted with more than 3 substituents.

For the third group of catalysts, examples of L² and L³ include, without limitation, heterocycles containing nitrogen, sulfur, oxygen, or a mixture thereof.

Examples of nitrogen-containing heterocycles appropriate for L² and L³ include pyridine, bipyridine, pyridazine, pyrimidine, bipyridamine, pyrazine, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, pyrrole, 2H-pyrrole, 3H-pyrrole, pyrazole, 2H-imidazole, 1,2,3-triazole, 1,2,4-triazole, indole, 3H-indole, 1H-isoindole, cyclopenta(b)pyridine, indazole, quinoline, bisquinoline, isoquinoline, bisisoquinoline, cinnoline, quinazoline, naphthyridine, piperidine, piperazine, pyrrolidine, pyrazolidine, quinuclidine, imidazolidine, picolylimine, purine, benzimidazole, bisimidazole, phenazine, acridine, and carbazole. Additionally, the nitrogen-containing heterocycles may be optionally substituted on a non-coordinating heteroatom with a non-hydrogen substitutent.

Examples of sulfur-containing heterocycles appropriate for L² and L³ include thiophene, 1,2-dithiole, 1,3-dithiole, thiepin, benzo(b)thiophene, benzo(c)thiophene, thionaphthene, dibenzothiophene, 2H-thiopyran, 4H-thiopyran, and thioanthrene.

Examples of oxygen-containing heterocycles appropriate for L² and L³ include 2H-pyran, 4H-pyran, 2-pyrone, 4-pyrone, 1,2-dioxin, 1,3-dioxin, oxepin, furan, 2H-1-benzopyran, coumarin, coumarone, chromene, chroman-4-one, isochromen-1-one, isochromen-3-one, xanthene, tetrahydrofuran, 1,4-dioxan, and dibenzofuran. Examples of mixed heterocycles appropriate for L² and L³ include isoxazole, oxazole, thiazole, isothiazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,3,4-oxadiazole, 1,2,3,4-oxatriazole, 1,2,3,5-oxatriazole, 3H-1,2,3-dioxazole, 3H-1,2-oxathiole, 1,3-oxathiole, 4H-1,2-oxazine, 2H-1,3-oxazine, 1,4-oxazine, 1,2,5-oxathiazine, o-isooxazine, phenoxazine, phenothiazine, pyrano[3,4-b]pyrrole, indoxazine, benzoxazole, anthranil, and morpholine.

Preferred L² and L³ ligands are aromatic nitrogen-containing and oxygen-containing heterocycles, and particularly preferred L² and L³ ligands are monocyclic N-heteroaryl ligands that are optionally substituted with 1 to 3, preferably 1 or 2, substituents. Specific examples of particularly preferred L² and L³ ligands are pyridine and substituted pyridines, such as 3-bromopyridine, 4-bromopyridine, 3,5-dibromopyridine, 2,4,6-tribromopyridine, 2,6-dibromopyridine, 3-chloropyridine, 4-chloropyridine, 3,5-dichloropyridine, 2,4,6-trichloropyridine, 2,6-dichloropyridine, 4-iodopyridine, 3,5-diiodopyridine, 3,5-dibromo-4-methylpyridine, 3,5-dichloro-4-methylpyridine, 3,5-dimethyl-4-bromopyridine, 3,5-dimethylpyridine, 4-methylpyridine, 3,5-diisopropylpyridine, 2,4,6-trimethylpyridine, 2,4,6-triisopropylpyridine, 4-(tert-butyl)pyridine, 4-phenylpyridine, 3,5-diphenylpyridine, 3,5-dichloro-4-phenylpyridine, and the like.

In general, any substituents present on either or both of L²L³ are selected from halo, C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀ heteroalkyl, C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl, C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, C₆-C₂₄ heteroalkaryl, substituted C₆-C₂₄ heteroalkaryl, C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, C₆-C₂₄ heteroaralkyl, substituted C₆-C₂₄ heteroaralkyl, and functional groups, with suitable functional groups including, without limitation, C₁-C₂₀ alkoxy, C₅-C₂₄ aryloxy, C₂-C₂₀ alkylcarbonyl, C₆-C₂₄ arylcarbonyl, C₂-C₂₀ alkylcarbonyloxy, C₆-C₂₄ arylcarbonyloxy, C₂-C₂₀ alkoxycarbonyl, C₆-C₂₄ aryloxycarbonyl, halocarbonyl, C₂-C₂₀ alkylcarbonato, C₆-C₂₄ arylcarbonato, carboxy, carboxylato, carbamoyl, mono-(C₁-C₂₀ alkyl)-substituted carbamoyl, di-(C₁-C₂₀ alkyl)-substituted carbamoyl, di-N—(C₁-C₂₀ alkyl), N—(C₅-C₂₄ aryl)-substituted carbamoyl, mono-(C₅-C₂₄ aryl)-substituted carbamoyl, di-(C₆-C₂₄ aryl)-substituted carbamoyl, thiocarbamoyl, mono-(C₁-C₂₀ alkyl)-substituted thiocarbamoyl, di-(C₁-C₂₀ alkyl)-substituted thiocarbamoyl, di-N—(C₁-C₂₀ alkyl)-N—(C₆-C₂₄ aryl)-substituted thiocarbamoyl, mono-(C₆-C₂₄ aryl)-substituted thiocarbamoyl, di-(C₆-C₂₄ aryl)-substituted thiocarbamoyl, carbamido, formyl, thioformyl, amino, mono-(C₁-C₂₀ alkyl)-substituted amino, di-(C₁-C₂₀ alkyl)-substituted amino, mono-(C₅-C₂₄ aryl)-substituted amino, di-(C₅-C₂₄ aryl)-substituted amino, di-N—(C₁-C₂₀ alkyl), N—(C₅-C₂₄ aryl)-substituted amino, C₂-C₂₀ alkylamido, C₆-C₂₄ arylamido, imino, C₁-C₂₀ alkylimino, C₅-C₂₄ arylimino, nitro, and nitroso. In addition, two adjacent substituents may be taken together to form a ring, generally a five- or six-membered alicyclic or aryl ring, optionally containing 1 to 3 heteroatoms and 1 to 3 substituents as above.

Preferred substituents on L² and L³ include, without limitation, halo, C₁-C₁₂ alkyl, substituted C₁-C₁₂ alkyl, C₁-C₁₂ heteroalkyl, substituted C₁-C₁₂ heteroalkyl, C₅-C₁₄ aryl, substituted C₅-C₁₄ aryl, C₅-C₁₄ heteroaryl, substituted C₅-C₁₄ heteroaryl, C₆-C₁₆ alkaryl, substituted C₆-C₁₆ alkaryl, C₆-C₁₆ heteroalkaryl, substituted C₆-C₁₆ heteroalkaryl, C₆-C₁₆ aralkyl, substituted C₆-C₁₆ aralkyl, C₆-C₁₆ heteroaralkyl, substituted C₆-C₁₆ heteroaralkyl, C₁-C₁₂ alkoxy, C₅-C₁₄ aryloxy, C₂-C₁₂ alkylcarbonyl, C₆-C₁₄ arylcarbonyl, C₂-C₁₂ alkylcarbonyloxy, C₆-C₁₄ arylcarbonyloxy, C₂-C₁₂ alkoxycarbonyl, C₆-C₁₄ aryloxycarbonyl, halocarbonyl, formyl, amino, mono-(C₁-C₁₂ alkyl)-substituted amino, di-(C₁-C₁₂ alkyl)-substituted amino, mono-(C₅-C₁₄ aryl)-substituted amino, di-(C₅-C₁₄ aryl)-substituted amino, and nitro.

Of the foregoing, the most preferred substituents are halo, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₁-C₆ alkoxy, phenyl, substituted phenyl, formyl, N,N-di(C₁-C₆ alkyl)amino, nitro, and nitrogen heterocycles as described above (including, for example, pyrrolidine, piperidine, piperazine, pyrazine, pyrimidine, pyridine, pyridazine, etc.).

In certain embodiments, L² and L³ may also be taken together to form a bidentate or multidentate ligand containing two or more, generally two, coordinating heteroatoms such as N, O, S, or P, with preferred such ligands being diimine ligands of the Brookhart type. One representative bidentate ligand has the structure of formula (VI)

wherein R¹⁵, R¹⁶, R¹⁷, and R¹⁸ hydrocarbyl (e.g., C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, or C₆-C₂₄ aralkyl), substituted hydrocarbyl (e.g., substituted C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, or C₆-C₂₄ aralkyl), heteroatom-containing hydrocarbyl (e.g., C₁-C₂₀ heteroalkyl, C₅-C₂₄ heteroaryl, heteroatom-containing C₆-C₂₄ aralkyl, or heteroatom-containing C₆-C₂₄ alkaryl), or substituted heteroatom-containing hydrocarbyl (e.g., substituted C₁-C₂₀ heteroalkyl, C₅-C₂₄ heteroaryl, heteroatom-containing C₆-C₂₄ aralkyl, or heteroatom-containing C₆-C₂₄ alkaryl), or (1) R¹⁵ and R¹⁶, (2) R¹⁷ and R¹⁸, (3) R¹⁶ and R¹⁷, or (4) both R¹⁵ and R¹⁶, and R¹⁷ and R¹⁸, may be taken together to form a ring, i.e., an N-heterocycle. Preferred cyclic groups in such a case are five- and six-membered rings, typically aromatic rings.

In a fourth group of catalysts that have the structure of formula (I), two of the substituents are taken together to form a bidentate ligand or a tridentate ligand. Examples of bidentate ligands include, but are not limited to, bisphosphines, dialkoxides, alkyldiketonates, and aryldiketonates. Specific examples include —P(Ph)₂CH₂CH₂P(Ph)₂-, —As(Ph)₂CH₂CH₂As(Ph₂)-, —P(Ph)₂CH₂CH₂C(CF₃)₂O—, binaphtholate dianions, pinacolate dianions, —P(CH₃)₂(CH₂)₂P(CH₃)₂—, and —OC(CH₃)₂(CH₃)₂CO—. Preferred bidentate ligands are —P(Ph)₂ CH₂CH₂P(Ph)₂- and —P(CH₃)₂(CH₂)₂P(CH₃)₂—. Tridentate ligands include, but are not limited to, (CH₃)₂NCH₂CH₂P(Ph)CH₂CH₂N(CH₃)₂. Other preferred tridentate ligands are those in which any three of X¹, X², L¹, L², L³, R¹, and R² (e.g., X¹, L¹, and L²) are taken together to be cyclopentadienyl, indenyl, or fluorenyl, each optionally substituted with C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₁-C₂₀ alkyl, C₅-C₂₀ aryl, C₁-C₂₀ alkoxy, C₂-C₂₀ alkenyloxy, C₂-C₂₀ alkynyloxy, C₅-C₂₀ aryloxy, C₂-C₂₀ alkoxycarbonyl, C₁-C₂₀ alkylthio, C₁-C₂₀ alkylsulfonyl, or C₁-C₂₀ alkylsulfinyl, each of which may be further substituted with C₁-C₆ alkyl, halide, C₁-C₆ alkoxy or with a phenyl group optionally substituted with halide, C₁-C₆ alkyl, or C₁-C₆ alkoxy. More preferably, in compounds of this type, X, L¹, and L² are taken together to be cyclopentadienyl or indenyl, each optionally substituted with vinyl, C₁-C₁₀ alkyl, C₅-C₂₀ aryl, C₁-C₁₀ carboxylate, C₂-C₁₀ alkoxycarbonyl, C₁-C₁₀ alkoxy, or C₅-C₂₀ aryloxy, each optionally substituted with C₁-C₆ alkyl, halide, C₁-C₆ alkoxy or with a phenyl group optionally substituted with halide, C₁-C₆ alkyl or C₁-C₆ alkoxy. Most preferably, X, L¹ and L² may be taken together to be cyclopentadienyl, optionally substituted with vinyl, hydrogen, methyl, or phenyl. Tetradentate ligands include, but are not limited to O₂C(CH₂)₂P(Ph)(CH₂)₂P(Ph)(CH₂)₂CO₂, phthalocyanines, and porphyrins.

Complexes wherein Y is coordinated to the metal are examples of a fifth group of catalysts, and are commonly called “Grubbs-Hoveyda” catalysts. Grubbs-Hoveyda metathesis-active metal carbene complexes may be described by the formula (VII)

wherein,

M is a Group 8 transition metal, particularly Ru or Os, or, more particularly, Ru;

X¹, X², and L¹ are as previously defined herein for the first and second groups of catalysts;

Y is a heteroatom selected from N, O, S, and P; preferably Y is O or N;

R⁵, R⁶, R⁷, and R⁸ are each, independently, selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroatom containing alkenyl, heteroalkenyl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, carbonyl, alkylamino, alkylthio, aminosulfonyl, monoalkylaminosulfonyl, dialkylaminosulfonyl, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, hydroxyl, ester, ether, amine, imine, amide, halogen-substituted amide, trifluoroamide, sulfide, disulfide, sulfonate, carbamate, silane, siloxane, phosphine, phosphate, borate, or -A-Fn, wherein “A” and Fn have been defined above; and any combination of Y, Z, R⁵, R⁶, R⁷, and R⁸ can be linked to form one or more cyclic groups;

n is 0, 1, or 2, such that n is 1 for the divalent heteroatoms O or S, and n is 2 for the trivalent heteroatoms N or P; and

Z is a group selected from hydrogen, alkyl, aryl, functionalized alkyl, functionalized aryl where the functional group(s) may independently be one or more or the following: alkoxy, aryloxy, halogen, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, hydroxyl, ester, ether, amine, imine, amide, trifluoroamide, sulfide, disulfide, carbamate, silane, siloxane, phosphine, phosphate, or borate; methyl, isopropyl, sec-butyl, t-butyl, neopentyl, benzyl, phenyl and trimethylsilyl. Additionally, R⁵, R⁶, R⁷, R⁸, and Z may independently be thioisocyanate, cyanato, or thiocyanato.

In general, Grubbs-Hoveyda complexes useful in the invention contain a chelating alkylidene moiety of the formula (VIII)

wherein Y, n, Z, R⁵, R⁶, R⁷, and R⁸ are as previously defined herein;

Y, Z, and R⁵ can optionally be linked to form a cyclic structure; and

R⁹ and R¹⁰ are each, independently, selected from hydrogen or a substituent group selected from alkyl, aryl, alkoxy, aryloxy, C₂-C₂₀ alkoxycarbonyl, or C₁-C₂₀ trialkylsilyl, wherein each of the substituent groups is substituted or unsubstituted. The chelating alkylidene moiety may be derived from a ligand precursor having the formula:

Non-limiting examples of complexes comprising Grubbs-Hoveyda ligands suitable in the invention include:

wherein, L¹, X¹, X², and M are as described for any of the other groups of catalysts. Suitable chelating carbenes and carbene precursors are further described by Pederson et al. (U.S. Pat. Nos. 7,026,495 and 6,620,955, the disclosures of both of which are incorporated herein by reference) and Hoveyda et al. (U.S. Pat. No. 6,921,735 and WO0214376, the disclosures of both of which are incorporated herein by reference).

Further examples of complexes having linked ligands include those having linkages between a neutral NHC ligand and an anionic ligand, a neutral NHC ligand and an alkylidine ligand, a neutral NHC ligand and an L² ligand, a neutral NHC ligand and an L³ ligand, an anionic ligand and an alkylidine ligand, and any combination thereof.

In addition to the catalysts that have the structure of formula (I), as described above, other transition metal carbene complexes include, but are not limited to:

neutral ruthenium or osmium metal carbene complexes containing metal centers that are formally in the +2 oxidation state, have an electron count of 16, are penta-coordinated, and are of the general formula (IX);

neutral ruthenium or osmium metal carbene complexes containing metal centers that are formally in the +2 oxidation state, have an electron count of 18, are hexa-coordinated, and are of the general formula (X);

cationic ruthenium or osmium metal carbene complexes containing metal centers that are formally in the +2 oxidation state, have an electron count of 14, are tetra-coordinated, and are of the general formula (XI); and

cationic ruthenium or osmium metal carbene complexes containing metal centers that are formally in the +2 oxidation state, have an electron count of 14 or 16, are tetra-coordinated or penta-coordinated, respectively, and are of the general formula (XII)

wherein:

M, X¹, X², L¹, L², L³, R¹, and R² are as defined for any of the previously defined four groups of catalysts;

r and s are independently zero or 1;

t is an integer in the range of zero to 5;

k is an integer in the range of zero to 1;

Y is any non-coordinating anion (e.g., a halide ion, BF₄ ⁻, etc.);

Z¹ and Z² are independently selected from —O—, —S—, —NR²—, —PR²—, —P(═O)R²—, —P(OR²)—, —P(═O)(OR²)—, —C(═O)—, —C(═O)O—, —OC(═O)—, —OC(═O)O—, —S(═O)—, —S(═O)₂—, —, and an optionally substituted and/or optionally heteroatom-containing C₁-C₂₀ hydrocarbylene linkage;

Z³ is any cationic moiety such as —P(R²)₃ ⁺ or —N(R²)₃ ⁺; and any two or more of X¹, X², L¹, L², L³, Z¹, Z², Z³, R¹, and R² may be taken together to form a cyclic group, e.g., a multidentate ligand.

Particularly useful catalysts include:

Additional catalyst embodiments are also described in WO 2012/097379 A2, “Z-Selective Olefin Metathesis Catalysts and their Synthetic Procedure,” which is incorporated by reference herein in its entirety. This reference describes a series of hindered metathesis catalyst that favor the formation of cis-bonds, and are useful for that purpose in the context of the present invention. These catalysts are described compound having a structure of Formula (XIII),

wherein

X¹ is an anionic ligand;

L¹ is a carbene ligand having the structure of Formula (XIV):

wherein,

Q is selected from hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, or substituted heteroatom-containing hydrocarbylene, wherein two or more substituents on adjacent atoms within Q may also be linked to form an additional cyclic structure;

R¹ is an optionally substituted hydrocarbylene or an optionally substituted heteroatom-containing hydrocarbylene, where R¹ links L¹ and M and, together with L¹ and M, form one or more cyclic groups, and wherein M, L¹ and R¹ form an M-R¹-L¹ chelating ligand ring structure having a ring size of 5, 6, or 7 atoms;

R² is an optionally substituted hydrocarbyl or an optionally substituted heteroatom-containing hydrocarbyl’

Y is N, O, S, or P (or other two electron donor);

R³, R⁴, R⁵, and R⁶ are each, independently, hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroatom containing alkenyl, heteroalkenyl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, carbonyl, alkylamino, alkylthio, aminosulfonyl, monoalkylaminosulfonyl, dialkylaminosulfonyl, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, hydroxyl, ester, ether, amine, imine, amide, halogen-substituted amide, trifluoroamide, sulfide, disulfide, sulfonate, carbamate, silane, siloxane, phosphine, phosphate, or borate, wherein any combination of R⁵, R⁶, R⁷, and R⁸ can be linked to form one or more cyclic groups;

n is 1 or 2, such that n is 1 for the divalent heteroatoms O or S, and n is 2 for the trivalent heteroatoms N or P; and

Z is selected from hydrogen, alkyl, aryl, functionalized alkyl, or functionalized aryl wherein the functional group(s) may independently comprise one or more or the following: alkoxy, aryloxy, halogen, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, hydroxyl, ester, ether, amine, imine, amide, trifluoroamide, sulfide, disulfide, carbamate, silane, siloxane, phosphine, phosphate, or borate; methyl, isopropyl, sec-butyl, t-butyl, neopentyl, benzyl, phenyl and trimethylsilyl; and wherein any combination or combinations of X¹, R¹, R², L¹, Y, Z, R³, R⁴, R⁵, and R⁶ are optionally linked to a support.

In other embodiments of Formula XIII, the methods employ hindered ruthenium metathesis catalysts of the structures above, wherein X¹ is halide, nitrate, alkyl, aryl, alkoxy, alkylcarboxylate, aryloxy, alkoxycarbonyl, aryloxycarbonyl, arylcarboxylate, acyl, acyloxy, alkylsulfonato, arylsulfonato, alkylsulfanyl, arylsulfanyl, alkylsulfinyl, or arylsulfinyl. In other embodiments, X¹ is a carboxylate, nitrate, phenoxide, bromide, chloride, iodide, sulfoxide, or nitrite. Nitrate and pivalate ligands are particularly suitable embodiments for the methods.

In the carbene ligand having the structure of Formula (XIV), Q is a linker, typically a hydrocarbylene linker, including substituted hydrocarbylene, heteroatom-containing hydrocarbylene, and substituted heteroatom-containing hydrocarbylene linkers, wherein two or more substituents on adjacent atoms within Q may also be linked to form an additional cyclic structure, which may be similarly substituted to provide a fused polycyclic structure of two to about five cyclic groups. Q is often, although again not necessarily, a two-atom linkage or a three-atom linkage. In more particular embodiments, Q is a two-atom linkage having the structure —CR¹¹R¹²—, —CR¹³R¹⁴— or —CR¹¹═CR¹³—, preferably —CR¹¹R¹²—CR¹³R¹⁴, wherein R¹¹, R¹², R¹³, and R¹⁴ are independently hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, or functional groups. Examples of suitable functional groups include carboxyl, C₁-C₂₀ alkoxy, C₅-C₂₄ aryloxy, C₂-C₂₀ alkoxycarbonyl, C₅-C₂₄ alkoxycarbonyl, C₂-C₂₄ acyloxy, C₁-C₂₀ alkylthio, C₅-C₂₄ arylthio, C₁-C₂₀ alkylsulfonyl, and C₁-C₂₀ alkylsulfinyl, optionally substituted with one or more moieties selected from C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy, C₅-C₁₄ aryl, hydroxyl, sulfhydryl, formyl, and halide. R¹¹, R¹², R¹³, and R¹⁴ are preferably independently selected from hydrogen, C₁-C₁₂ alkyl, substituted C₁-C₁₂ alkyl, C₁-C₁₂ heteroalkyl, substituted C₁-C₁₂ heteroalkyl, phenyl, and substituted phenyl. Alternatively, any two of R¹¹, R¹², R¹³, and R¹⁴ may be linked together to form a substituted or unsubstituted, saturated or unsaturated ring structure, e.g., a C₄-C₁₂ alicyclic group or a C₅ or C₆ aryl group, which may itself be substituted, e.g., with linked or fused alicyclic or aromatic groups, or with other substituents. In one further aspect, any one or more of R¹¹, R¹², R¹³, and R¹⁴ comprises one or more of the linkers.

In certain embodiments, R¹ is an optionally substituted alkylene, optionally substituted heteroatom-containing alkylene, optionally substituted cycloalkylene, optionally substituted heteroatom-containing cycloalkylene, optionally substituted aryl, or optionally substituted heteroaryl. In other embodiments, R¹ is an optionally substituted cycloalkylene or optionally substituted aryl. R¹ may also be an optionally substituted adamantylene group or a substituted C₃-C₁₂ cycloalkylene group. Adamantylene is a particularly suitable R¹ moiety.

In still other embodiments of Formula XII, R¹ is an optionally substituted cycloalkyne, an optionally substituted heteroatom-containing cycloalkylene, an optionally substituted aryl, or an optionally substituted heteroaryl and R² is an optionally substituted cycloalkyl, an optionally substituted heteroatom-containing cycloalkyl, an optionally substituted aryl, or an optionally substituted heteroaryl. Further embodiments provide that R¹ is an optionally substituted cycloalkylene and R² is a substituted aryl group. When R² is a substituted aryl group, certain embodiments provide that one or both ortho positions are substituted, preferably by methyl, ethyl, propyl, or isopropyl substitutents. Under these conditions, the other meta or para-positions may also be substituted. Suitable substituent patterns include those where R² is 2,4,6-trimethyl phenyl (mesityl), methylisopropylphenyl (MIPP), or di-isopropylphenyl (DIPP).

In some embodiments of Formula XIII, Q is an optionally substituted ethylene (—CH₂CH₂—), R¹ is an optionally substituted adamantylene, R² is 2,4,6-trimethyl phenyl (mesityl), 2-methyl, 6-isopropylphenyl (MIPP), or 2,6-diisopropylphenyl (DIPP); X¹ is nitrate or pivalate, R³, R⁴, R⁵, and R⁶ are each hydrogen; Y is O; and (Z)_(n) is isopropyl.

Accordingly, suitable C—H activated olefin metathesis catalyst compound also comprise one or more of the following:

In general, the transition metal complexes used as catalysts herein can be prepared by several different methods, such as those described by Schwab et al. (1996) J. Am. Chem. Soc. 118:100-110, Scholl et al. (1999) Org. Lett. 6:953-956, Sanford et al. (2001) J. Am. Chem. Soc. 123:749-750, U.S. Pat. No. 5,312,940, and U.S. Pat. No. 5,342,909, the disclosures of each of which are incorporated herein by reference. Also see U.S. Pat. Pub. No. 2003/0055262 to Grubbs et al., filed Apr. 16, 2002, for “Group 8 Transition Metal Carbene Complexes as Enantioselective Olefin Metathesis Catalysts,” International Patent Publication No. WO 02/079208, and U.S. Pat. No. 6,613,910 to Grubbs et al., filed Apr. 2, 2002, for “One-Pot Synthesis of Group 8 Transition Metal Carbene Complexes Useful as Olefin Metathesis Catalysts,” the disclosures of each of which are incorporated herein by reference. Preferred synthetic methods are described in International Patent Publication No. WO 03/11455A1 to Grubbs et al. for “Hexacoordinated Ruthenium or Osmium Metal Carbene Metathesis Catalysts,” published Feb. 13, 2003, the disclosure of which is incorporated herein by reference.

Polymer Compositions

To this point, the invention has largely been described in terms of methods of making polymer compositions, though some aspects of the resulting polymer compositions have been described. For the sake of clarity, however, the invention contemplates and certain embodiments include those compositions that comprise at least one polymer prepared in whole or in part by any one of the inventive methods described herein. These include, without limitation, those compositions comprising only a single polymer, or a plurality of individual polymer strands, whether free-standing or tethered to a substrate surface. These embodiments also include homopolymers and random or block co-polymers that may or may not be capable of conducting electrons, or behaving as semiconductors, or both.

Devices

The present disclosure also contemplates those devices and portions thereof which take advantage of the teachings presented here. That is, certain embodiments include those devices comprising one or more polymers prepared in whole or in part by any of the methods described herein. These include, as non-limiting examples, polymer electronic devices (e.g. diodes, capacitors, chemical sensors, light emitting diodes (LEDs), photodetectors, photovoltaic cells, thermoelectric detectors, or transistors), medical implants, composite materials, antireflection coatings, antifouling coatings, microfluidics, and reactor modifications for chemical syntheses, especially, but not limited to, those which benefit from the described advantages of the polymer compositions which result from the methods.

The following listing of embodiments in intended to complement, rather than displace or supersede, the previous descriptions.

Embodiment 1

A method of metathesizing unsaturated organic compounds, said method comprising contacting at least one feedstock vapor or gas comprising at least one olefinic or acetylenic precursor with a solid transition metal-based metathesis catalyst to form a polymer product, wherein the transition metal-based metathesis catalyst is in a solid form and the contacting is done in the absence of a liquid.

Embodiment 2

The method of Embodiment 1, wherein the olefinic or acetylenic precursor is presented to the solid transition metal-based metathesis catalyst as a vapor or gas.

Embodiment 3

The method of Embodiments 1 or 2, wherein the product polymer is formed by an enyne, a diyne, or ring opening metathesis polymerization (ROMP) reaction.

Embodiment 4

The method of any one of the preceding Embodiments, wherein the olefinic or acetylenic precursor comprises a cis- or trans-alkene or alkyne linkage.

Embodiment 5

The method of any one of the preceding Embodiments, wherein the olefinic or acetylenic precursor comprises a linear acetylenic compound.

Embodiment 6

The method of any one of the preceding Embodiments, wherein the linear acetylenic compound comprises acetylene, H—C≡C—H.

Embodiment 7

The method of any one of the preceding Embodiments, where the product comprises a polyacetylene polymer or polymer block.

Embodiment 8

The method of any one of the preceding Embodiments, wherein the polyacetylene comprises a cis-polyacetylene polymer or polymer block.

Embodiment 9

The method of any one of the preceding Embodiments, wherein the polyacetylene comprises a trans-polyacetylene polymer or polymer block.

Embodiment 10

The method of any one of the preceding Embodiments, wherein any one of the at least one feedstock comprises a single olefinic or acetylenic precursor.

Embodiment 11

The method of any one of the preceding Embodiments, wherein any one of the at least one feedstock comprises at least two olefinic or acetylenic precursor.

Embodiment 12

The method of any one of Embodiments 1-5 or 7-11, wherein any one of the at least one of the olefinic or acetylenic precursors contains an electron donor substituent, such that the precursor, when polymerized, is capable of forming a semiconducting polymer or polymer block that acts as an electron donor.

Embodiment 13

The method of any one of Embodiments 1-5 or 7-11, wherein any one of the at least one of the olefinic or acetylenic precursors contains an electron acceptor substituent, such that the precursor, when polymerized, is capable of forming a semiconducting polymer or polymer block that acts as an electron acceptor.

Embodiment 14

The method of any one of the preceding Embodiments, wherein two or more feedstocks are sequentially contacted with the solid transition metal-based metathesis catalyst.

Embodiment 15

The method of any one of the preceding Embodiments, wherein the metathesis reaction is carried out under conditions where the at least one olefinic or acetylenic precursor has a partial pressure in a range of about 1 psia to about 200 psia.

Embodiment 16

The method of any one of the preceding Embodiments, wherein the metathesis reaction is carried out at a temperature in a range of about −10° C. to about 300° C.

Embodiment 17

The method of any one of the preceding Embodiments, further comprising depositing nanoparticles on the polymer product.

Embodiment 18

The method of any one of the preceding Embodiments, further comprising co-depositing nanoparticles during the metathesis reaction.

Embodiment 19

The method of any one of the preceding Embodiments, further comprising depositing iodine on the polymer product.

Embodiment 20

The method of any one of the preceding Embodiments, further comprising pre-reacting a second end-functionalized olefinic or acetylenic precursor with a surface, under conditions sufficient to attached the end-functionalized olefinic or acetylenic precursor to the surface.

Embodiment 21

The method of Embodiment 20, wherein the second end-functionalized olefinic or acetylenic precursor is attached to a surface by covalent bonding, hydrogen bonding, ionic bonding, physisorption, pi-pi interaction, Van der Waals forces, or a combination thereof.

Embodiment 22

The method of Embodiment 20 or 21, further comprising contacting the attached second end-functionalized olefinic or acetylenic precursor with the transition metal-based metathesis catalyst dissolved in a solvent and then removing the solvent.

Embodiment 23

The method of any one of Embodiments 20 to 22, wherein the surface is a metal, metalloid, or an inorganic or metallic oxide.

Embodiment 24

The method of any one of Embodiments 20 to 23, wherein one end of the polymer product is attached to the surface, and the polymer product is oriented to extend from the surface, the end of the polymer attached to the surface being the proximal end and the other end of the polymer being the distal end.

Embodiment 25

The method of Embodiment 24, wherein the transition metal-based metathesis catalyst is bonded to the distal end of the polymer product.

Embodiment 26

The method of any one of Embodiments 20 to 25, wherein the polymer product comprises a plurality of individual polymer strands, each polymer strand attached to and oriented to extend from the surface.

Embodiment 27

The method of any one of Embodiments 20 to 26 wherein the polymer product comprises a plurality of individual polymer strands aligned substantially parallel to one another.

Embodiment 28

The method of any one of the preceding Embodiments, wherein the transition metal-based metathesis catalyst comprises Mo, Ru, Ta, Ti, or W.

Embodiment 29

The method of any one of the preceding Embodiments, wherein the transition metal-based metathesis catalyst comprises ruthenium.

Embodiment 30

The method of any one of the preceding Embodiments, wherein the transition metal-based metathesis catalyst comprises a N-heterocyclic carbene compound of ruthenium.

Embodiment 31

The method of any one of the preceding Embodiments, wherein the transition metal-based metathesis catalyst is a Grubbs-type ruthenium catalyst.

Embodiment 32

The method of any one of the preceding Embodiments, wherein the transition metal-based metathesis catalyst is a Second Generation Grubbs-type ruthenium catalyst.

Embodiment 33

The method of any one of the preceding Embodiments, wherein the transition metal-based metathesis catalyst is

Embodiment 34

A method of metathesizing acetylene, according to any one of the preceding claims, said method comprising contacting gaseous acetylene, H—C≡C—H, with a solid Second Generation Grubbs-type ruthenium catalyst to form a polyacetylene polymer or polymer block, the interface between the acetylene and the catalyst being a direct gas/solid phase interface.

Embodiment 35

A composition comprising at least one polymer prepared by a method of any one of the preceding Embodiments.

Embodiment 36

The composition of Embodiment 35, wherein the composition comprises a plurality of individual polymer strands.

Embodiment 37

The composition of Embodiment 35 or 36, wherein the composition is capable of conducting electrons.

Embodiment 38

The composition of any one of Embodiments 35 to 37, wherein the composition is capable of exhibiting semiconductor behavior.

Embodiment 39

A device comprising a composition of any one of Embodiments 35 to 38.

Embodiment 40

The device of Embodiments 39, wherein the device is a diode, capacitor, chemical sensor, light emitting diode (LED), microfluidic device, photodetector, photovoltaic cell, thermoelectric detector, transistor, medical implant, or comprises an antireflection coatings or antifouling coating.

EXAMPLES

The following Examples are provided to illustrate some of the concepts described within this disclosure. While each Example is considered to provide specific individual embodiments of composition, methods of preparation and use, none of the Examples should be considered to limit the more general embodiments described herein.

In the following examples, efforts have been made to ensure accuracy with respect to numbers used (e.g. amounts, temperature, etc.) but some experimental error and deviation should be accounted for. Unless indicated otherwise, temperature is in degrees C., pressure is at or near atmospheric.

Example 1 Materials and Methods

All glassware was oven dried and reactions were performed under ambient conditions unless otherwise noted. All solvents and reagents were purchased from commercial suppliers and used as received unless otherwise noted.

In the following examples, Catalyst 1 and Catalyst 2 refer to:

Example 2 Preparation of Physisorbed Films of Polyacetylene

Using a pipette, 0.5 ml of a solution of 14 mg of Catalyst 1 in 1 mL toluene was transferred onto a glass slide. The flat-bottomed Schlenk flask containing the sample was evacuated slowly to 120 millitorr, and backfilled with 5 psia of acetylene gas. The sample was allowed to react at ambient room temperature for 15 hours, after which it was quenched and rinsed with ethyl vinyl ether. Color changed from green to yellow to red to black as the polyacetylene chain length increased over several hours. The matte black polyacetylene films produced were verified by surface Fourier transform infrared spectroscopy.

In a second experiment, a 1.0 mg/mL solution of Catalyst 1 in acetone was deposited onto a silicon coupon, wetting the entire surface, all within a “Fischer-Porter” glass pressure vessel. The acetone was slowly removed by evacuating the vessel at 2.0 torr. A light green film was deposited on the surface. The chamber was further evacuated to 100 millitorr, then backfilled with 5 psia acetylene gas. The reaction was stopped at 26 hours by evacuating the chamber. A black layer of polyacetylene was present on the silicon surface. The sample was cleaved under argon for scanning electron microscopy analysis. The images show measured thicknesses of the polyacetylene film of approximately 700-1500 nm.

Example 3 Preparation of Covalently Tethered Polyacetylene

Silicon coupons (2 cm×2 cm) were cleaned with piranha solution (70:30 H₂SO₄:H₂O₂) for one hour, rinsed with DI water, methanol and acetone, and dried under argon. A monolayer of pent-5-enyl phosphonic acid was prepared by the method described in Hanson, et al., Journal of the American Chemical Society 2003, 125, 16074-16080 from a solution in THF (structure of tethered complex illustrated in FIG. 1). In a nitrogen-filled glove box, the functionalized coupon was placed into a solution of 25 mg of Catalyst 2 in 2 mL of toluene, which was held under static vacuum for 10 minutes. The coupon was removed and submerged into fresh toluene, rinsed with ˜10 mL of toluene, and allowed to dry. The coupon was placed in a flat-bottomed Schlenk flask, which was evacuated to 150 millitorr and backfilled with 5 psia acetylene gas and held at ambient room temperature for 16 hours. Dark black crystallites were observed by optical microscopy (FIG. 2). These crystallites were contacted with a metal probe tip to provide an example of a complete device, where the silicon substrate served as one electrode, and the probe tip as the other.

Example 4 Demonstration of a Polyacetylene Schottky Diode

Inside of a “Fischer-Porter” glass pressure vessel, a 1.0 mg/mL solution of Catalyst 1 in acetone was deposited onto an aluminum-coated silicon coupon, wetting the entire surface. The acetone was slowly removed by evacuating the vessel at 2.0 torr. A light green film was deposited on the surface. The chamber was further evacuated to 400 millitorr, then backfilled with 5 psia acetylene gas. The reaction was allowed to proceed at ambient room temperature and was stopped at 13 hours by evacuating the chamber. The sample was annealed at 175° C. at 200 millitorr for 5 minutes, to isomerize any cis-polyacetylene to trans-polyacetylene.

A fluorine-doped tin oxide electrode (TEC 15 grade, on glass, from Sigma Aldrich) was cleaned in boiling acetone. Under a blanket of argon, this electrode was used to make a pressure contact to the polyacetylene on Al by holding the two sides together with binder clips. See FIG. 3A for an illustration of the prepared structure Afterwards, the device was kept and characterized inside a custom-made Schlenk vessel with tungsten rods beaded through the glass, for use as electrodes. The connections between each electrode and the tungsten rods, as well as the connections between the tungsten rods and the source meter unit were made using standard wires with alligator-clips. The device was characterized using a Keithley source meter unit and custom software, while sealed at 200 millitorr. The current-voltage measurement is presented in FIG. 3C. The data can be extrapolated to fit a non-ideal diode equation with a dark current J0=1.96×10-8 A/cm2 and a diode ideality factor n=5.01. The data showed clear evidence of rectification. See FIGS. 3B and 3C.

As those skilled in the art will appreciate, numerous modifications and variations of the present invention are possible in light of these teachings, and all such are contemplated hereby. For example, in addition to the embodiments described herein, the present invention contemplates and claims those inventions resulting from the combination of features of the invention cited herein and those of the cited prior art references which complement the features of the present invention. Similarly, it will be appreciated that any described material, feature, or article may be used in combination with any other material, feature, or article, and such combinations are considered within the scope of this invention.

The disclosures of each patent, patent application, and publication cited or described in this document are hereby incorporated herein by reference, each in its entirety, for all purposes. 

What is claimed:
 1. A method of metathesizing unsaturated organic compounds, said method comprising contacting at least one feedstock vapor or gas comprising at least one acetylenic precursor with a solid transition metal-based metathesis catalyst to form a polymer product, wherein the transition metal-based metathesis catalyst is in a solid form and the contacting is done in the absence of a liquid.
 2. The method of claim 1, wherein the acetylenic precursor is presented to the solid transition metal-based metathesis catalyst as a gas.
 3. The method of claim 1, wherein the product polymer is formed by an enyne, a diyne, or ring opening metathesis polymerization (ROMP) reaction.
 4. The method of claim 1, wherein the acetylenic precursor comprises a linear acetylenic compound.
 5. The method of claim 1, wherein the acetylenic precursor is acetylene, H—C≡C—H.
 6. The method of claim 1, where the polymer product comprises a polyacetylene polymer or block.
 7. The method of claim 1, wherein the polymer product comprises a trans-polyacetylene polymer or block.
 8. The method of claim 1, wherein any one of the at least one feedstock comprises a single acetylenic precursor.
 9. The method of claim 1, wherein any one of the at least one feedstock comprises at least two acetylenic precursors.
 10. The method of claim 1, further comprising further contacting at least one feedstock gas comprising at least one olefinic precursor with a solid transition metal-based metathesis catalyst to form a polymer product, wherein the transition metal-based metathesis catalyst is in a solid form and the contacting is done in the absence of a liquid.
 11. The method of claim 10, wherein any one of the at least one of the olefinic or acetylenic precursors contains an electron acceptor substituent, such that the precursor, when polymerized, is capable of forming a semiconducting polymer or polymer block that acts as an electron acceptor.
 12. The method of claim 10, wherein two or more feedstocks are sequentially contacted with the solid transition metal-based metathesis catalyst.
 13. The method of claim 1, comprising contacting the at least one feedstock gas comprising at least acetylenic precursor with a solid transition metal-based metathesis catalyst under conditions where the at least one acetylenic precursor has a partial pressure in a range of from about 1 psia to about 200 psia.
 14. The method of claim 1, comprising contacting the at least one feedstock gas comprising at least one acetylenic precursor with a solid transition metal-based metathesis catalyst at a temperature in a range of from about −10° C. to about 300° C.
 15. The method of claim 1, further comprising depositing iodine on the polymer product.
 16. The method of claim 1, further comprising pre-reacting a second olefinic or acetylenic precursor with a surface, the second olefinic or acetylenic precursor being end-functionalized, under conditions sufficient to attached the end-functionalized olefinic or acetylenic precursor to the surface.
 17. The method of claim 16, wherein the second end-functionalized olefinic or acetylenic precursor is attached to a surface by covalent bonding, hydrogen bonding, ionic bonding, physisorption, pi-pi interaction, Van der Waals forces, or a combination thereof.
 18. The method of claim 16, further comprising contacting the attached second end-functionalized olefinic or acetylenic precursor with the transition metal-based metathesis catalyst dissolved in a solvent and then removing the solvent.
 19. The method of claim 16, wherein the surface is a metal, metalloid, or an inorganic or metallic oxide.
 20. The method of claim 16, wherein one end of the polymer product, the polymer product having proximal and distal ends, is attached to the surface, and the polymer product is oriented to extend from the surface, the end of the polymer attached to the surface being the proximal end and the other end of the polymer being the distal end.
 21. The method of claim 20, wherein the transition metal-based metathesis catalyst is bonded to the distal end of the polymer product.
 22. The method of claim 16, wherein the polymer product comprises a plurality of individual polymer strands, each polymer strand attached to and oriented to extend from the surface.
 23. The method of claim 16, wherein the polymer product comprises a plurality of individual polymer strands aligned substantially parallel to one another.
 24. The method of claim 1, wherein the transition metal-based metathesis catalyst is a Grubbs-type ruthenium catalyst.
 25. The method of claim 1, wherein the transition metal-based metathesis catalyst is a Second Generation Grubbs-type ruthenium catalyst.
 26. The method of claim 1, wherein the transition metal-based metathesis catalyst is


27. The method of claim 1, said method comprising contacting gaseous acetylene, H—C≡C—H, with a solid Second Generation Grubbs-type ruthenium catalyst to form a polyacetylene polymer or polymer block, the interface between the acetylene and the catalyst being a direct gas/solid phase interface.
 28. The method of claim 10, wherein any one of the at least one of the olefinic or acetylenic precursors contains an electron donor substituent, such that the precursor, when polymerized, is capable of forming a semiconducting polymer or polymer block that acts as an electron donor. 